A new photoluminescence (PL) band (N) with Emax = Eg + Δ in MBE‐GaAs films is observed. It is found that the N band intensity correlates with the quality of the MBE film structure. Photoluminescence and photoluminescence excitation spectra of the N band are investigated as well as the dependence of the N band on exciting light intensity, temperature, surface conditions, elastic stresses, and electric field. Some probable explanations of the N band origin are presented.