In this paper, we report the preparation and characterization of composites of polypyrrole (PPy) with polyvinylidene fluoride (PVDF), and cellulose. We used the techniques of chemical and electrochemical polymerization. These materials were characterized using X-ray diffraction (wide and small angle (SAXS)), electrical conductivity and electron microscopy. The studies showed that homogeneous composites could be formed. The percentage crystallinity of the host polymer decreased, whereas some crystallization of PPy was noticed. SAXS studies revealed that the diffusion of PPy is in amorphous regions. The electrical conductivity of the composites was found to vary in the range of 10(-8) S/cm to 10(-4) S/cm. These composites were found to be useful in gas sensors for detection of chlorine and ammonia.