Poly(4-vinylpyridine) was crosslinked and quaternized with 1,4-bromobutane to form a polyelectrolyte humidity sensitive film on an interdigitated gold electrode, which was further coated with a layer of polypyrrole by a facile method of vapor phase polymerization. The composite so prepared was characterized by UV–vis spectroscopy and scanning electron microscopy. The investigations on the humidity sensitive properties of the composite revealed that it exhibited an impedance as low as 10 5 Ω even at 0%RH due to the existence of intrinsic conducting polypyrrole, thus conquering the difficulties in measuring low humidity with resistive-type humidity sensors. The impedance of the composite changed linearly with humidity in the range of 0–60%RH with good sensitivity. In addition, its response time ( t 90%) for adsorption and desorption between 33% and 97%RH was estimated to be 33 s and 110 s, respectively, and a hysteresis of 5%RH was observed. All these suggest it is promising as a sensitive material for low humidity detection. The effect of concentration and ratio of oxidizing agent to doping agent, polymerization temperature of pyrrole on the humidity sensitive properties of the composite have been investigated. A sensitive mechanism of the composite was proposed by taking into account the contribution of both the intrinsic electronic conduction and ionic conduction.