"Yesterday (Thursday) we received a letter from the technical director rescinding his contract," said Jorge Gimenez, president of the Venezuelan Football Federation.
"We spoke with him in the evening and explained to him that it was difficult for us to understand his position... because we have a triple-header," said Gimenez.
It was not enough to change Peseiro's mind, though, and he confirmed his resignation on Friday morning.
South American minnows Venezuela face Argentina, Peru and Paraguay in World Cup qualifiers between September 2 and September 9.
They sit second from the bottom of the single 10-team Conmebol qualifying group in which the top four will book tickets for the 2022 finals in Qatar, while the fifth-placed finishers will head into an inter-continental play-off.
Peseiro was appointed in February 2020, just before the coronavirus pandemic broke out.
Gimenez said Peseiro was owed "no more and no less than one year" of salary, adding that "he's hardly been paid anything from his tenure."
Peseiro oversaw one win, three draws and six defeats as the "Vinotinto" coach.
No replacement has yet been named.
Venezuela is the only member of Conmebol never to have qualified for a World Cup.
The country is in the midst of the worst economic crisis in its modern history, having suffered eight years of recession, including the last four years of hyperinflation.