Strong electron spin polarization in GaNAs epilayers and multiple quantum well structures is observed upon optical orientation at room temperature. The effect is explained in terms of spin dependent recombination (SDR) involving deep paramagnetic defects formed upon N incorporation in GaNAs. Concentration of the corresponding defects is shown to be enhanced during growth at low temperatures but is suppressed by post-growth annealing. Optically detected magnetic resonance (ODMR) measurements performed in the studied structures reveal two paramagnetic defects participating in carrier recombination. One of them is identified as a complex involving AsGa antisite. Correlation between concentrations of the defects monitored via ODMR and in optical orientation measurements is observed which suggests that the same defects may be involved in both processes.