This was to try to end fighting that has left the world's newest state on the brink of civil war.
The talks in neighbouring Ethiopia will focus on brokering a ceasefire to halt three weeks of ethnic violence that has killed at least a thousand people and driven 200,000 from their homes.
"We have begun our meeting on the cessation of hostilities," a member of the government delegation told Reuters.
The fighting, often along ethnic faultlines, has pitted President Salva Kiir's SPLA government forces against rebels loyal to former vice president Riek Machar.
Mabior Garang, a member of Machar's delegation to the Addis talks, confirmed that the talks had begun.