Efficient and stable photocathodes with versatility are of significance in photoassisted lithium-ion batteries (PLIBs), while there is always a request on fast carrier transport in electrochemical active photocathodes. Present work proposes a general approach of creating bulk heterojunction to boost the carrier mobility of photocathodes by simply laser assisted embedding of plasmonic nanocrystals. When employed in PLIBs, it was found effective for synchronously enhanced photocharge separation and transport in light charging process. Additionally, experimental photon spectroscopy, finite difference time domain method simulation and theoretical analyses demonstrate that the improved carrier dynamics are driven by the plasmonic-induced hot electron injection from metal to TiO2, as well as the enhanced conductivity in TiO2 matrix due to the formation of oxygen vacancies after Schottky contact. Benefiting from these merits, several benchmark values in performance of TiO2-based photocathode applied in PLIBs are set, including the capacity of 276 mAh g−1 at 0.2 A g−1 under illumination, photoconversion efficiency of 1.276% at 3 A g−1, less capacity and Columbic efficiency loss even through 200 cycles. These results exemplify the potential of the bulk heterojunction strategy in developing highly efficient and stable photoassisted energy storage systems.