A woman kicks at a riot police shield as relatives of prisoners wait to hear news about their family members imprisoned at a police station where a riot broke out, in Valencia. Picture: Juan Carlos Hernandez/AP

Caracas - Five high-ranking police officers have been arrested in Venezuela following the deaths of 68 inmates in a prison riot, local media reported.

Those named in the arrest warrants issued by Venezuela's Attorney General Tarek William Saab included the deputy chief of police of Carabobo state, El Carabobeno newspaper reported late Saturday.

On Wednesday, a fire broke out following a riot at a makeshift prison in the regional capital Valencia's police headquarters, killing 66 men and two women, local authorities said.

Some 200 inmates at the police headquarters were being held in cells meant to accommodate 35 people.

READ: 68 dead in Venezuela prison riot

Initial investigations found that the inmates set fire to mattresses in order to force officers to open their cells. The victims died as a result of smoke inhalation and burns.

The UN Human Rights Office has demanded that those responsible for the events at the police station be named and brought before a court, according to statement released in Geneva. The statement also called for prison conditions in the South American country to be significantly improved.

The prison riot in Carabobo state was the second-deadliest in Venezuela's history. In 1994, 108 people died in a riot in the country's Zulia state.