In the last years, the development of photocatalysts has gained a growing interest in the photoelectrochemical conversion. Here, we report a hetero-junction organic/inorganic (Polyaniline (PANI)) on n type Silicon substrate prepared by electrophoretic deposition (EPD). ZnO nanorods (NRs) are grown by chemical bath deposition (CBD) on seed layer of ZnO prepared by dip coating onto the PANI layer. The relief and morphological properties are investigated by both atomic force microscope (AFM) and scanning electron microscopy (SEM). The forbidden bands (Eg) of 1.12 and 3.26 eV are obtained for PANI and ZnONRS respectively. The optical and dielectric constants are determined by the diffuse reflectance where the extinction coefficient (k), the refractive index (n), optical conductivity, dissipation factor and relaxation time are extracted. The semi conductivity is highlighted by the capacitance measurement; a flat band potential (Efb = 0.541 V) for ZnONRs-PANI is deduced from the Mott-Schottky plot. The contributions of the bulk and grain boundaries of the electrode are evidenced from the electrochemical impedance spectroscopy (EIS). The as-fabricated samples show improved photoactivity compared to PANI and ZnONRs. Indeed, the hetero-junction exhibits a high stability and recyclability for the photodegradation of Orange II (OII) after six cycling runs. The current research offers a new understanding of designing a high performance of the photocatalyst under solar light based on PANI for the wastewater treatment.