Geison Valero belonged to the opposition party First Justice and Omar Fernandez was an independent.
The First Justice party said they were campaigning for opposition leader Henrique Capriles in Barinas state when gunmen shot them dead.
Witnesses said the vehicle belonged to the state oil company PDVSA.
But there has been no confirmation of this from the Venezuelan authorities.
A statement by the party said a rally had been planned in Barinas, President Hugo Chavez's home state, but the road was blocked by government supporters.
When the two men left their car to try to gain access, they were fired on by gunmen inside a van, it said.
Both Mr Chavez's and Mr Capriles are wrapping up their campaigns over the next few days ahead of the 7 October elections.
There have been other incidents of violence on the campaign trail. Supporters of both candidates threw stones at each other earlier this month when Mr Capriles attempted to march through the city of Puerto Cabello.
And four people were injured in a shooting that erupted during a voting rehearsal at the beginning of September.
With violent crime a key concern for voters, the BBC's Sarah Grainger in Caracas says there are fears that further violence could erupt in what has become Venezuela's closest fought election in over a decade.
Mr Chavez's has been in power since 1999, but was diagnosed with cancer last year.
More than 30 opposition parties have backed a single candidate, Henrique Capriles, to challenge the leftist president.
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