In this research, the investigation of sensing properties of non-stoichiometric WO3 (WO3−x) film towards some volatile organic compounds (VOC) (namely: Methanol, ethanol, isopropanol, acetone) and ammonia gas are reported. Sensors were tested at several temperatures within the interval ranging from a relatively low temperature of 60 up to 270 °C. Significant variation of selectivity, which depended on the operational temperature of sensor, was observed. Here, the reported WO3/WO3–x-based sensing material opens an avenue for the design of sensors with temperature-dependent sensitivity, which can be applied in the design of new gas- and/or VOC-sensing systems that are dedicated for the determination of particular gas- and/or VOC-based analyte concentration in the mixture of different gases and/or VOCs, using multivariate analysis of variance (MANOVA).