The major drawback of oxide-based sensors is the lack of selectivity. In this context, Sn x Ti 1−x O 2 /graphene oxide (GO)-based materials were synthesized via a simple hydrothermal route, varying the titanium content in the tin dioxide matrix. Then, toluene and acetone gas sensing performances of the as-prepared sensors were systematically investigated. Specifically, by using 32:1 SnO 2 /GO and 32:1 TiO 2 /GO, a greater selectivity towards acetone analyte, also at room temperature, was obtained even at ppb level. However, solid solutions possessing a higher content of tin relative to titanium (as 32:1 Sn 0.55 Ti 0.45 O 2 /GO) exhibited higher selectivity towards bigger and non-polar molecules (such as toluene) at 350 • C, rather than acetone. A deep experimental investigation of structural (XRPD and Raman), morphological (SEM, TEM, BET surface area and pores volume) and surface (XPS analyses) properties allowed us to give a feasible explanation of the different selectivity. Moreover, by exploiting the UV light, the lowest operating temperature to obtain a significant and reliable signal was 250 • C, keeping the greater selectivity to the toluene analyte. Hence, the feasibility of tuning the chemical selectivity by engineering the relative amount of SnO 2 and TiO 2 is a promising feature that may guide the future development of miniaturized chemoresistors.