This report provides a proof of concept for the realization of an organic pyroelectric nanogenerator which encompasses the fabrication and study of charge driven π-conjugated hetero-system by pyrophototronic effect. A rectifying junction is created with polycrystalline graphene-based material, and crystalline polyaniline-rubrene thin-film which belongs to the aromatic class of organic materials where light-induced change in surface layer polarization helps the device to achieve pyroelectric behavior. The fabricated device is self-sustainable and can generate current as well as voltage in self-powered mode. Overall, this work reveals the viable alternatives and new perspectives for harnessing power from organic materials to realize an organic pyroelectric nanogenerator.