The optically detected magnetic resonance technique is applied to determine the nature of broad, featureless emission bands observed in the near‐infrared region in bulk GaP crystals grown by the liquid encapsulated Czochralski method. A broad emission band with maximum at ≊8000 A˚ (≊1.55 eV) was consistently observed in undoped and donor‐doped (S, Te, Se, Ge) crystals, and is shown to be due to donor‐acceptor pair (DAP) recombination. The analysis of the optically detected magnetic resonance experiments indicates that shallow donors and deep acceptors are active in the 8000‐A˚ recombination. The identity of the ≊0.7‐eV deep acceptor center active in this DAP transition could not be determined from the experimental results, but a single acceptor complex consisting of a Ga vacancy and two adjacent donors is proposed as a tentative model.