"There are ideological differences at the heart of the government," Livni told public radio.
The stalling of the peace process since September 2010 "only serves the interests of those think that each passing day (without a peace agreement) allows them to build a new house," she said, in reference to Jewish settlement building on Palestinian territory, a key issue preventing a return to talks.
"But this is not the position of the majority of Israel's population," she added.
Kerry is to meet Prime Minister Benjamin Netanyahu, President Shimon Peres and will travel to Ramallah to meet Palestinian president Mahmud Abbas.
Israel's coalition government, headed by the Likud party's Netanyahu, also includes the rightwing nationalist Jewish Home and the centrist Yesh Atid, which oppose concessions on settlement building, the cessation of which is a Palestinian precondition for any peace talks.