Room temperature operated sensor for detection of alcohol vapours in low ppm range based on TiO2 functionalized nano-porous silicon (PSi) is demonstrated. The effect of functionalization by TiO2 on PSi is investigated using SEM, EDX, Raman spectroscopy, XRD and contact angle measurements. Sensing is accomplished by measuring change in resistance of the sensing layer using Cr-Au inter-digitated-electrode (IDE) structure formed on top of the functionalized PSi layer. The sensors were tested for volatile organic compounds (VOCs) and water vapours in the wide range of 5–500 ppm concentration at room temperature. Functionalization of the nanostructured PSi by sputter deposited TiO2 results in significant enhancement of sensitivity and inverse change in selectivity. PSi sensors have displayed strong response to water vapours whereas after functionalization, selective sensing to ethanol is depicted. Minimum detection by PSi sensors is portrayed at 100 ppm and that of functionalized sensors is at 10 ppm. Sensing mechanism is explained on the basis of surfaces and structures of both PSi and TiO2. This study incites the importance of surface treatment of PSi for tuning the sensing properties and is useful in the development of selective alcohol sensors. © 2016