Pure and Sm3+ (0.33, 0.46, 1.48, and 2.19 at.%)-doped ZrO2 thin films have been prepared using radio-frequency (RF) sputtering technique. The phase composition and photoluminescence (PL) properties have been studied on these pure and doped thin films as a function of annealing temperature and doping concentration. Phase composition analysis indicates the increment in the monoclinic content and crystallite size of the pure sample with the increase in annealing temperature. Higher doping promotes the tetragonal phase of the material. From PL studies, Sm3+ (0.33 at.%)-doped zirconia thin film shows a stronger emission spectra than other higher doping. All doped samples exhibit a well-resolved emission series of Sm3+ at higher annealing temperatures. The effect of structural modifications on the PL spectra of the zirconia system has been investigated. Monoclinic phase promotes the luminescence efficiency of this system. PL study shows one to one correspondence with that of structural modification of zirconia system.