Kidman arrived in Kosovo's capital, Pristina, after attending the premiere of her new movie "Fur" at the inaugural Rome film festival. She was scheduled to spend two days in the province.
"I'm here ... to learn so that I can help your country at this crucial, crucial time for the future," Kidman said.
"To meet people, hear their stories and educate myself, and I suppose be a voice for you if you need it."
Dressed in black pants and a blouse, Kidman shook hands with Kosovo's top UN official, Joachim Ruecker, dozens of local leaders and diplomats attending a welcome reception.
She was named goodwill ambassador of the UN development fund for women, or UNIFEM, in January, and the tour of Kosovo is her first visit in that role.
After the reception Kidman was cheered by crowds of onlookers as
she walked through the centre of town to her hotel.
The Hollywood star is expected to travel tomorrow to the south-western town of Djakovica, among the hardest hit areas during the 1998-1999 war. About 1,000 men went missing from the town in the conflict.
Kosovo, which formally remains part of Serbia, has been run by a UN mission since mid-1999, when NATO forced Serb forces to halt a crackdown on independence-seeking ethnic Albanians.
Kidman visited the province at a sensitive time, with ethnic Albanians and Serbs are engaged in tense negotiations over the future status of Kosovo.
Ethnic Albanians want full independence for the province of 2 million, while Serbia insists Kosovo should remain under its sovereignty.