We report Ag nanoparticles infused with mesosphere TiO2/reduced graphene oxide (rGO) nanosheet (TiO2/rGO/Ag) hybrid nanostructures have been successfully fabricated using a series of solution process synthesis routes and an in-situ growth method. The prepared hybrid nanostructure is utilized for the fabrication of photovoltaic cells and the photocatalytic degradation of pollutants. The photovoltaic characteristics of a dye-sensitized solar cell (DSSC) device with plasmonic hybrid nanostructure (TiO2/rGO/Ag) photoanode achieved a highest short-circuit current density (JSC) of 16.05 mA/cm2, an open circuit voltage (VOC) of 0.74 V and a fill factor (FF) of 62.5%. The fabricated plasmonic DSSC device exhibited a maximum power conversion efficiency (PCE) of 7.27%, which is almost 1.7 times higher than the TiO2-based DSSC (4.10%). For the photocatalytic degradation of pollutants, the prepared TiO2/rGO/Ag photocatalyst exhibited superior photodegradation of methylene blue (MB) dye molecules at around 93% and the mineralization of total organic compounds (TOC) by 80% in aqueous solution after 160 min under continuous irradiation with natural sunlight. Moreover, the enhanced performance of the DSSC device and the MB dye degradation exhibited by the hybrid nanostructures are more associated with their high surface area. Therefore, the proposed plasmonic hybrid nanostructure system is a further development for photovoltaics and environmental remediation applications.