Zinc tungstate crystal scintillator is an interesting detector material for double beta decay, dark matter, and rare alpha decay experiments. The luminescence under X-ray excitation in the temperature region from 85 K to 420 K was studied with five samples of ZnWO4 crystals developed by different methods: with a stoichiometric composition, and with excess of Zn or W. It is found that doping a ZnWO4 crystal with 0.2–0.3% Zn and W does not affect the luminescence properties of the material. A theoretical dependence of the sample luminescence intensity on the competing nonradiative recombination centers and traps is obtained. The main center of the recombination luminescence in a ZnWO4 crystal with a spectral maximum at 2.5 eV is the tungsten complex with a structural defect located next to it.