Krishna Prasad Situala, the home (interior) minister, before entering the talks as head of a three-member government team, on Friday said: "We will discuss everything that is of interest to Nepal and its people.
"I am 100% confident that the talks will be successful."
Shortly after he spoke, the three-man Maoist team arrived at the Gokarna Forest Golf Resort and Spa, just outside the capital, Kathmandu, but declined to talk to reporters.
Earlier, a Maoist negotiator, Dev Gurung, had welcomed Thursday's cabinet decision to free hundreds of jailed rebels and investigate cases of people reported to have disappeared after being detained by security forces.
"This has helped ease the atmosphere and build confidence," he said.
The first round of talks is supposed to prepare the ground for a meeting between Prachanda, the Maoist rebels' chief, and Girija Prasad Koirala, the prime minister.
Hopes for peace have risen since a new multi-party government took power last month after weeks of street protests against King Gyanendra.
A ceasefire was agreed earlier this month.
Maoists had entered a loose alliance with the seven main political parties last year against the king, agreeing on a 12-point plan to end royal rule and bring peace to the Himalayan nation.
"There is a confidence between us and the Maoists now," the interior minister told reporters when asked why he was so confident.
"We have a 12-point understanding with them - that is the basis of our confidence. There are no complexities."
Nepal's new parliament has already agreed to a main rebel demand, to hold elections for a special assembly to draft a new constitution and decide the future of the monarchy.
Situala said the talks would focus on how to conduct those elections, and the government wanted to hold them as soon as possible.
Despite the minister's confidence, some observers say the question of disarmament remains a potential sticking point.
The insurgency has claimed more than 13,000 lives and wrecked the economy of the impoverished Himalayan country.
Previous peace talks failed in 2001 and 2003.