The foreign minister also signed agreements on educational and technical exchanges with US officials.
The upbeat pronouncements on Thursday were, however, shadowed by concerns about human rights and unfinished legal issues stemming from bombings in the 1980s.
Relations were held back after Libya, which was implicated in the 1988 Lockerbie bombing in Scotland and that of a German disco in 1986, failed to settle the compensation to families of the victims.
The US state department said Rice raised the settlement of past cases, human rights and geopolitical issues in the one-hour talk with Shalgam.
"Secretary Rice urged Libya to move forward in resolving outstanding claims by families of terror victims against the Libyan government and raised human rights as an important agenda item for our bilateral relationship," Sean McCormack, a department spokesman, said.
US officials also separately raised the case of Fathi al-Jahmi, a political activist jailed in 2004 for openly criticising Muammar Gaddafi, the Libyan leader.
Human rights groups had asked Rice to raise the case of political prisoners, torture and other documented abuses.
Sarah Leah Whitson, Human Rights Watch's Middle East and North Africa director, said the warming of ties should not be "at the expense of political prisoners, torture victims, and other Libyans who suffer abuse".