Single crystals of intrinsic ZnSe were grown by the seeded physical vapor transport method and the diffusion doping was utilized to incorporate Cr in these crystals. The radiative recombinations in these samples with Cr concentration in the range 1.0–10.2×1019 cm−3 were studied by the steady state photoluminescence technique. It was found that the Cr deep centers inhibit the band-to-band emission in Cr-doped ZnSe. Except in undoped single crystals, no emission corresponding to the band-to-band transition was observed from any of the doped samples. Instead, the higher wavelength emissions associated with Cr deep levels were obtained. This capture of photoexcited carriers by deep centers was verified using different excitation wavelengths. The role of chromium impurities in nonradiative recombination processes was also evidenced from the sharp decreases in the deep level emission intensity with increasing Cr concentration.