Talks are scheduled to begin at 5pm AEST, with acting Prime Minister Phumtham Wechayachai leading the Thai negotiating team, the government announced in a statement.
Malaysia, which chairs the ASEAN regional co-operation forum, has informed the Thai government that Cambodian Prime Minister Hun Manet would also be attending the talks, the statement said.
Tensions between Thailand and Cambodia have intensified since the late-May killing of a Cambodian soldier during a brief border skirmish. Border troops on both sides were reinforced amid a full-blown diplomatic crisis that brought Thailand's fragile coalition government to the brink of collapse.
Hostilities resumed on Thursday and, within just four days, escalated into the worst fighting between the Southeast Asian neighbours in more than a decade.
The death toll has risen above 30, including 13 civilians in Thailand and eight in Cambodia, while authorities report that more than 200,000 people have been evacuated from border areas.
Monday's talks come after Malaysian Prime Minister Anwar Ibrahim last week proposed a ceasefire and US President Donald Trump said on Saturday that the two leaders had agreed to work on a ceasefire.
Secretary of State Marco Rubio said State Department officials were in Malaysia to assist peace efforts.
"We want this conflict to end as soon as possible," he said.
Bangkok and Phnom Penh have each accused the other side of sparking last week's hostilities.
Cambodia's Defence Ministry said Thailand had shelled and launched ground assaults on Sunday morning at a number of points along the border. The ministry's spokesperson said heavy artillery was fired at historic temple complexes.
The Thai army said Cambodian forces had fired shots into several areas, including near civilian homes, on Sunday, and were mobilising long-range rocket launchers.
"The situation remains tense and Cambodian troops may be preparing intensified military operations to inflict maximum damage in the final stages before negotiations," the army said in an update.
In the Thai province of Sisaket, Reuters reporters heard shelling throughout Sunday and said it was unclear which side of the border it was on.
A government health clinic about 10km from the border had shattered windows, collapsed walls and exposed wiring. Local media reported it was hit by artillery on Saturday, two days after the building and surrounding neighbourhood was evacuated.
Thailand and Cambodia have bickered for decades over undemarcated points along their 817km land border, with ownership of the ancient Hindu temples Ta Moan Thom and the 11th century Preah Vihear central to the disputes.
Preah Vihear was awarded to Cambodia by the International Court of Justice in 1962, but the situation worsened in 2008 after Cambodia attempted to list it as a UNESCO World Heritage site. Skirmishes over several years brought at least a dozen deaths.
Cambodia said in June it had asked the International Court of Justice to resolve its disputes with Thailand. Bangkok says it has never recognised the court's jurisdiction and prefers a bilateral approach.
