But he added that "for constitutional reasons, the aircraft employed in this humanitarian mission should carry the emblems of the International Red Cross".
Chavez had revealed his plan to secure the freedom of the hostages held by Revolutionary Armed Forces of Colombia (Farc) at a news conference in Caracas.
The process for the release "has been agreed to the tiniest detail with the Farc commanders," said Chavez, who has been involved in mediation.
The Venezuelan leader offered to send aircraft to pick up the hostages, who include an aide to prominent French-Colombian hostage Ingrid Betancourt.
He added that he hoped that all other hostages held by the Farc, including Betancourt, would also be released.
Theresa Bo, reporting for Al Jazeera from Caracas, said the Farc wanted to release the hostages in a way that would benefit Chavez as much as possible.
Talks between the Farc and Alvaro Uribe, Colombia's conservative president, over the conditions under which the three would be released.
|Clara Rojas is among those hoping to be|
freed in the coming days [AFP]
Chavez was told by Uribe last month to stay out of hostage negotiations with Farc, but he has continued to talk to the rebels.
The Farc, a self-proclaimed communist revolutionary group, said a week ago they would free three hostages: Clara Rojas, her son Emmanuel, who was born in captivity from her relationship with a Farc fighter, and Consuelo Gonzalez de Perdomo, a Colombia legislator.
Ivan Rojas said in Colombia that he supports Chavez's plan to secure the release of his sister.
"We are very optimistic that this will turn out well," he said.
Rojas has been a captive since 2002, when she was seized alongside Betancourt as she campaigned for president.
Perdomo was kidnapped in 2001.
Meanwhile a nine-year-old boy who was kidnapped by armed men claiming to be Farc fighters has been rescued by Colombian police.
The kidnapping happened in May at his family's farm, when suspected Farc guerrillas entered the home and asked for room and board.
They then took the boy and demanded $50,000 in ransom for his release, an amount his family could not pay.
On Tuesday, police raided a house in the city of Neiva, found the boy and arrested two Farc fighters.
"I was enclosed. The food was awful, and I was only allowed to eat once a day," the boy, whose identity was not revealed, told Bogota's El Tiempo newspaper in an interview published on Wednesday.
"They insulted me and said they were going to kill me."
Some 2,567 children and teens have been kidnapped in Colombia in the past 12 years, including 60 in 2007, according to Pais Libre, a foundation dedicated to supporting kidnapping victims.