A nanocrystalline and porous p-polyaniline/n-WO3 dissimilar heterojunction at ambient temperature is reported. The high-quality and well-reproducible conjugated polymer composite films have been fabricated by oxidative polymerization of anilinium ion on predeposited WO3 thin film by chemical bath deposition followed by thermal annealing at 573 K for 1 h. Atomic force microscopy (AFM) analyses reveal a homogenous but irregular cluster of faceted spherically shaped grains with pores. The scanning electron microscopy confirms the porous network of grains, which is in good agreement with the AFM result. The optical absorption analysis of polyaniline/WO3 hybrid films showed that direct optical transition exist in the photon energy range 3.50–4.00 eV with bandgap of 3.70 eV. The refractive index developed peak at 445 nm in the dispersion region while the high-frequency dielectric constant, ɛ∞, and the carrier concentration to effective mass ratio, N/m*, was found to be 1.58 and 1.10 × 1039 cm−3, respectively. The temperature dependence of electrical resistivity of the deposited films follows the semiconductor behavior while the C–V characteristics (Mott–Schottky plots) show that the flat band potential was −791 and 830 meV/SCE for WO3 and polyaniline.