Ozone detection is currently the subject of wide scientific and technological research, motivated by its harmful impact on human safety, environment and health. With the aim of searching for new highly sensitive materials for ozone detection, Ga-doped ZnS and ZnS–ZnO films were deposited by a spray pyrolysis technique. The obtained films were annealed at 400 °C for two hours. The ozone sensing properties were investigated by measuring the sensor resistance for several ozone concentrations ranging from 30 to 120 ppb. The sensor response reveals a dependence on the gallium concentration. The best response was obtained with 4% doping gallium. The sensitivity is 4.5 ppb−1 at 260 °C and the response to 30 ppb ozone is 150. Moreover, the sensor shows high performance such as good selectivity and fast rapidity.