In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0wt.% (as blank), 0.1, 1, and 10wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5ppm(v). The adsorption/desorption behavior was also examined at humidity concentration 510.2ppm(v). The sensitivities of 0, 0.1 and 1wt.% Ppy films at 51.5ppm(v) were 0.143, 0.219 and 0.427, respectively. For 1wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R(2)) for 1wt.% Ppy at the ranges of 14.7-898.6ppm(v) were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be approximately 3kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1wt.% Ppy film explains higher sensitivity.