Four people died at Shikenge village in the Kavango East region after two vehicles collided on Sunday.
One vehicle belongs to the Namibian Correctional Service (NCS) while the other is a seven-seater.
The Namibian Police's crime investigations coordinator in the region, deputy commissioner Bonifasius Kanyetu, confirmed the accident on Tuesday, saying the NCS vehicle immediately caught fire after the impact.
Witnesses at the accident scene extinguished the fire.
Kanyetu said it is alleged that the NCS vehicle was travelling at high speed when it collided with the seven-seater.
The two NCS officials in the vehicle, Angala Eliakim Natangwe (39) and Njuva Samson (49), died in the fire. Their next of kin have been informed.
Kanyetu said the two NCS employees were returning from an official trip to the Divundu Correctional Facility.
The deceased people from the seven-seater have been identified as Anton Shinkanda and Nduva Elizabeth Mbangu (34). Their next of kin have also been informed.
Police investigations into the matter continue.