Hybrid multi-functional nanomaterials comprising two or more disparate materials have become a powerful approach to obtain advanced materials for environmental remediation applications. In this work, an Ag-Ag 2 O/TiO 2 @polypyrrole (Ag/TiO 2 @PPy) heterojunction has been synthesized by assembling a self-stabilized Ag-Ag 2 O (p type) semiconductor (denoted as Ag) and polypyrrole (π-conjugated polymer) on the surface of rutile TiO 2 (n type). Ag/TiO 2 @PPy was synthesized through simultaneous oxidation of pyrrole monomers and reduction of AgNO 3 in an aqueous solution containing well-dispersed TiO 2 particles. Thus synthesized Ag/TiO 2 @PPy was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and UV-Vis diffuse reflectance spectroscopy (UV-vis DSR). The photocatalytic activity of synthesized heterojunction was investigated for the decomposition of methylene blue (MB) dye under UV and visible light irradiation. The results revealed that π-conjugated p-n heterojunction formed in the case of Ag/TiO 2 @PPy significantly enhanced the photodecomposition of MB compared to the p-n type Ag/TiO 2 and TiO 2 @PPy (n-π) heterojunctions. A synergistic effect between Ag-Ag 2 O and PPy leads to higher photostability and a better electron/hole separation leads to an enhanced photocatalytic activity of Ag/TiO 2 @PPy under both UV and visible light irradiations.