We report on the low cost and low temperature chemical synthesis of p-type nickel oxide (NiO) and n-type reduced graphene oxide (rGO) and their integration onto ITO/glass substrate to form p-NiO/n-rGO heterojunction for possible self-powered ultraviolet (UV) photodetector applications. Different spectroscopies and microscopes were employed to study their microstructural and surface properties. Whereas, the electrical characterizations have been performed on the devices to ascertain the responsivity, detectivity, external quantum efficiency and temporal responses under dark and UV illumination. It is noteworthy that rGO has not only been used as an n-type semiconductor, but also acted as an electron transport layer, which satisfactorily separates out the electrons from the generated carrier pairs, leading to enhanced photoresponse. Furthermore, efforts were also consecrated to synthesize Ag nanoparticles (NPs) of ∼5 nm radius. The integration of Ag NPs on the conventional NiO/rGO heterojunction facilitates an improved UV light absorption property. It was understood that the performance improvement was owed to the local surface plasmon resonance of Ag NPs within the active layer of NiO. Surprisingly, both the devices (with and without Ag NPs) exhibit photovoltaic behavior which shows its potential for self-powered device application. When the Ag NPs embedded device is concerned, it showed better on/off ratio (6.3 × 10), high responsivity (72 mAW), large detectivity (3.95 × 10 Jones), and high efficiency (24.46%) as compared to the conventional NiO/rGO heterojunction one (without Ag NPs). The variation in the photoresponse and improved charge transport was explained through a band-diagram, which also showcases a comprehensive understanding on the operational principle of the fabricated self-powered devices. Thus, this self-powered photodetector driven by built in electric field is operated independently and can be attached with any other electronic gadgets for internet of things applications.