A composite of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and zinc stannate (ZnSnO3) has been introduced for impedance-based humidity sensing, owing to its high sensitivity, good stability, very fast response (similar to 0.2 s) and recovery time (similar to 0.2 s), small hysteresis, repeatability, low-cost fabrication and wide range of sensitivity. Both materials were mixed in three different weight percentage ratios, to optimize the performance of the sensors. Best response was observed for 5 wt.% PEDOT:PSS and 5 wt.% ZnSnO3. The impedance of the sensor was dropped immensely from 1.5 M Omega to 50 k Omega by changing relative humidity from 0% to 90%. The reason for this improvement in sensitivity was analyzed by virtue of sensing mechanisms and different characterizations (three dimensional (3D) nano-profiler, optical microscope, and fourier transform infra-red (FTIR) spectroscopy) revealing the surface morphology and chemical structure of the film. Due to its response and ability to sense human breath and skin humidity, it is suitable for environmental, artificial skin and food industry applications.