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But she pointed out the "suffering" caused by the North African country's long stand-off with the West.
Libya was on the US state department list of sponsors of terrorism until 2003, when it abandoned weapons of mass destruction and renounced terrorism.
Ms Rice will be the first US secretary of state to visit Libya since 1953.
"It is a historic moment and it is one that has come after a lot of difficulty, the suffering of many people that will never be forgotten or assuaged," Ms Rice told a news conference in Lisbon, Portugal, before leaving for Libya.
Her trip will also include visits to Tunisia, Algeria and Morocco.
But the visit could be overshadowed by Libya's failure so far to honour a deal offering compensation to families of victims of the 1988 Lockerbie bombing.
The BBC's Rana Jawad in Tripoli says that six years ago, such a visit would have seemed far-fetched, but diplomacy and political will have overcome the obstacles.
The US State Department have described it as a "new chapter" in relations between the two countries, following on from the restoration of diplomatic ties in 2006.
'Way forward'
Earlier this month, Libya agreed to pay compensation to families of the victims of the Lockerbie aircraft bombing, for which it formally accepted responsibility in 2003.
The deal includes compensation for Libyan victims of the United States' retaliatory bombing raid over Libya in 1986.
Ms Rice's visit was partly intended to be a reward for successful completion of the deal, but Libya has not yet transferred the promised hundreds of millions of dollars into a humanitarian account.
The US Assistant Secretary of State for Near Eastern Affairs, David Welch, told Reuters that he was optimistic the transfer would happen soon but that Ms Rice would press Libya on this issue.
Col Gaddafi has stopped short of referring to America as a friend, but in a televised speech this week he said improved relations were a way for both countries to leave each other alone.
Assistant Secretary of State Paula DeSutter told a briefing in Washington on Thursday that the visit would show other countries they have "a way forward" if they change their behaviour and co-operate with the US.
Our correspondent says that although the visit is largely symbolic diplomacy, many in Libya hope that US-Libyan relations will only improve in the long-run.
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(BBC)
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