Israeli media said Shamir had suffered from Alzheimer's for years and died after a long illness Saturday at a nursing home in the town of Herzliya, north of Tel Aviv.
In his younger days, Shamir served as a Jewish underground leader who fought the British as well as Arab militias before Israel's creation in 1948. Later, he hunted Nazi scientists as a Mossad agent before eventually becoming Israel's seventh prime minister.
His time in office was eventful, marked by the massive airlift of thousands of Ethiopian Jews to Israel, the Palestinian uprising and the 1991 Gulf war, when Iraq fired 39 Scud missiles at Israel.
Israelis across the political spectrum paid tribute to the former leader Saturday.
“Yitzhak Shamir was a brave warrior before and after the founding of the State of Israel,” said Israeli President Shimon Peres, a longtime political opponent of Shamir.
“He was loyal to his views, a great patriot and a true lover of Israel who served his country with integrity and unending commitment. May his memory be blessed.”
Prime Minister Benjamin Netanyahu said “led Israel with a deep loyalty to the nation and to the land and to the eternal values of the Jewish people.”
Shamir served as premier for seven years, from 1983-84 and 1986-92, leading his party to election victories twice, despite lacking much of the outward charisma that characterizes many modern politicians.
Barely over five feet (1.52m) tall and built like a block of granite, he projected an image of uncompromising solidity during the first intifada, or Palestinian uprising, in the West Bank and Gaza that demanded an end to Israeli occupation.
Defeated in the 1992 election, Shamir stepped down as head of the Likud party and watched from the sidelines as his successor, Yitzhak Rabin, negotiated interim land-for-peace agreements with the Palestinians.
The agreements, including Palestinian leader Yasser Arafat's recognition of Israel, did nothing to ease his suspicion.
In a 1997 interview with the New York-based Jewish Post, he declared: “The Arabs will always dream to destroy us. I do not believe that they will recognize us as part of this region.”
The Labor movement, in power for Israel's first three decades, agreed to a 1947 U.N.-proposed partition plan to allow the creation of the Jewish state alongside a Palestinian entity. To Shamir, that was tantamount to treason.
Born Yitzhak Jazernicki in what is now Poland in 1915. Shamir moved to pre-state Palestine in 1935. Most of his family stayed behind and was killed in the Holocaust during World War II.
Once in Palestine, Shamir joined LEHI, the most hardline of three Jewish movements fighting for independence from the British mandate authorities, taking over the group's leadership after the British killed its founder.
LEHI was behind the assassination of United Nations mediator Count Folke Bernadotte in Jerusalem in September 1948. LEHI commanders considered Bernadotte to be a British agent who cooperated with the Nazis.
Shamir often disguised himself as an orthodox rabbi to avoid arrest by the British. Still, he was captured twice, but escaped from two British detention camps and returned to resistance action. The second camp was in Djibouti, in Africa.
After Israel was founded in 1948, Shamir went into business before entering a career in Israel's Mossad spy agency.
During that time, he carried out operations against Nazi scientists who were helping Israel's Arab neighbors build rockets. Roni Milo, a former member of parliament who served under Shamir mourned his passing to Israeli TV.
“For years he served in the Mossad and oversaw many important operations,” Milo said. “I once asked him about a street name while walking in Tel Aviv and Shamir said ‘I know the streets of Cairo and Damascus better than the streets of Tel Aviv.”'
In the mid-1960s he emerged to join the right-wing Herut party, which evolved into the present-day Likud.
Shamir succeeded Menahem Begin as prime minister in 1983 in the aftermath of Israel's disastrous 1982 invasion of Lebanon.
His term was marked by the massive airlift of thousands of Ethiopian Jews to Israel, the Palestinian uprising and the 1991 Gulf war, when Iraq fired 39 Scud missiles at Israel.
During the Gulf war, Shamir went along with American demands not to retaliate for the Iraqi missile strikes. After the war, the United States stepped up pressure to start a Middle East process that could lead in only one direction—compromise with the Arabs.
Exasperated by Shamir's stubborn refusal to go along with their plans for a regional settlement, then-U.S. Secretary of State James Baker once went on television, recited the switchboard number of the White House and told Shamir to call when he got serious about peace.
In the end, American pressure bent even Shamir. Despite his deep mistrust of Arab intentions, he agreed to attend the 1991 Middle East peace conference in Madrid, sponsored by the U.S. and Russia.
Shamir hotly rejected the deals his successors made with the Palestinians, in which Israel turned over control of some West Bank land to the Palestinians.
His pleasure at the 1996 election victory of Likud leader Benjamin Netanyahu soured when Netanyahu continued to negotiate with the Palestinians and carry out land-for-security deals.
Before the 1999 election, Shamir resigned from the Likud and joined a new right-wing block called National Union, headed by Begin's son, Ze'ev Binyamin.
The party, which rejected any turnover of land to the Palestinians, won only four seats in parliament, though it had seven members of the outgoing legislature on its list.
In 2001, Shamir was given his nation's highest civilian honor, the Israel Prize awarded annually to outstanding citizens in several fields.
“Dad was an amazing man,” Shamir's daughter, Gilada, told the Israeli news site Ynet. “He was a family man in the fullest sense of the word, a man who dedicated himself to the State of Israel but never forgot his family, not even for a moment.”
Israeli media said a funeral would be held Monday. Knesset speaker Reuven Rivlin said the funeral procession would leave from Israel's parliament.