Structural aspects, such as grain size, pore size, and crack-free film morphology, of porous silicon (PS), etc., play a vital role in the sensing of volatile organic compounds (VOCs). This chapter discusses a novel method for sensing of VOCs using porous silicon coated with a layer of ZnO (PS-ZnO). It was noted that the sensing ability of the PS sensor has increased due to the transconductance mechanism, as a result of the coating of ZnO over PS. Initially, porous silicon is formed by electrochemical wet etching of silicon and by electrophoretic deposition (EPD), ZnO is coated over porous silicon. An increase in the selectivity is due to the increase in surface-to-volume ratio and uniformity in the pore structures. The thickness of ZnO layer can be tuned up to 25 nm by applying a DC voltage between the copper electrode and the conductive silicon substrate immersed in a suspension of ZnO quantum dots. The influence of quantum dot concentration on the final layer thickness was studied by X-ray diffraction (XRD). The change in resistance for ethanol was found to be 12.8-16 MΩ and 8-16 MΩ for methanol.