Bogota and the National Liberation Army (ELN) last week kicked off a six-month ceasefire as negotiations aiming to end decades of armed conflict continue.
The talks in Venezuela are the fourth round of discussions since President Gustavo Petro resumed negotiations with the country's last active guerilla group in November last year.
Pablo Beltran, head of the ELN delegation, called for the discussions to result in "humanitarian aid for populations and towns that are suffering the most."
Government negotiator Otty Patino also dedicated the latest round of talks to those "living in areas affected by abandonment and violence."
The talks will take place in Caracas until September 4.
Colombia has suffered more than half a century of armed conflict between the state and various left-wing guerrilla groups, right-wing paramilitaries and drug traffickers.
The ELN started as a leftist ideological movement in 1964 before turning to crime, focusing on kidnapping, extortion, violent attacks and drug trafficking in Colombia and neighboring Venezuela.
With some 5,800 combatants, the group is primarily active in the Pacific region and along the 2,200-kilometer (1,370-mile) border with Venezuela.
Official data shows the ELN has a presence in more than 200 municipalities, where fighting has led to people being displaced, or confined to specific areas -- notably because of the use of anti-personnel mines hampering their movement.
At the end of May, some 1,500 people, mainly from Indigenous communities, had to flee their territory in western Choco, due to fighting between the ELN and The Gulf Clan, the country's biggest drug gang.
The ELN became the oldest armed group in the Americas after the disarmament of the Revolutionary Armed Forces of Colombia (FARC) in 2017.
Last week the ELN denied accusations it was plotting to kill Attorney General Francisco Barbosa, who said he had received a tip-off about the plan.
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