We investigated the role of surface etching in the process of laser-induced generation of nitrogen–vacancy (NV) complexes in diamond. The diamond treatment was performed using 100 fs laser pulses at wavelengths of 800, 400, and 266 nm, with a laser fluence that was lower than the graphitization threshold. The data characterizing the effect of irradiation dose and laser fluence on NV centres photoluminescence intensity are presented. The experiments conducted show a clear correlation between the photoluminescence emission, enhanced because of irradiation, and the amount of carbon material removed from the surface in this process. The mechanism combining laser-induced vacancy creation at the crystal surface and the plasma-assisted diffusion of the vacancies into the crystal bulk is discussed.