"We have been informed by the Red Cross that the operation to free (hostage ex-lawmaker Odin Sanchez) has begun," said Juan Camilo Restrepo, the government's chief negotiator for the talks.
The negotiations had been due to formally open at 5:00 pm (local time) until President Juan Manuel Santos suspended them with just hours to go because of the dispute over Sanchez.
Restrepo said he believed the hostage handover would be completed by November 3, when the first round of actual negotiations had been scheduled to begin.
The International Committee of the Red Cross often facilitates the handover of hostages from Colombian rebel groups after their release has been agreed.
It was not immediately clear how long Sanchez's release would take.
Santos earlier said the talks could not begin "until (the rebels) release Odin Sanchez safe and sound."
The president, who won the Nobel Peace Prize this month, is working on two fronts to end a half-century conflict gripping Colombia.
His government is also in talks with a larger rebel group, the FARC. The two sides are racing to save a peace deal that voters rejected in a referendum this month.
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