The ZnAl2O4:Co 2+ powders with the low Co 2+ dopant concentrations (0.5 at.%) have been synthesized by hydrothermal method using the following precursors: zinc chloride (ZnCl2), aluminium chloride (AlCl3·6H2O), cobalt nitrate (Co(NO3)2), urea (CO(NH2)2), ethanol (C2H5OH) and sodium hydroxide (NaOH). The effect of the amounts of NaOH, CO(NH2)2 and thermal treatment conditions on formatting the ZnAl2O4 structure and their optical properties were investigated. The results showed that the structure and the size of ZnAl2O4 crystallites strongly depended on the amount of NaOH, CO(NH2)2 and thermal treatment conditions. The photoluminescence and photoluminescence excitation spectra of the samples strongly depended on the thermal treatment conditions. For the samples which did not undergo thermal treatment, their optical properties almost did not depend on the amounts of CO(NH2)2. For the samples undergone thermal treatment at 800• C and 1200• C, the photoluminescence and photoluminescence excitation spectra were totally changed. They strongly depended on the excitation wavelength and amount of urea in the initial sample synthesis process.