The move comes after Queiroz was banned for six months following his interruption of a doping testing session, despite Queiroz himself claiming relations with the Portuguese Football Federation "have always been great" only yesterday.
Gilberto Madail, the president of the PFF has confirmed the move in a brief statement to Reuters, "Carlos Queiroz's contract is settled [ended] with immediate effect".
The Federation had originally given the coach a one month suspension in late August, only for Portugal's anti-doping authority to extend the ban to six months.
Queiroz and his Portuguese international players were the subject of a surprise, yet routine, visit by anti-doping doctors in late May, and the 57-year-old has admitted to agressive verbal behaviour in their presence.
Queiroz claimed he was purely expressing his annoyance at the unannounced visit as it interrupted his players' rest, and is determined to appeal against the ban at the Court of Arbitration for Sport.