• A universal bulk heterojunction strategy is developed to create oxygen vacancies by embedding laser-manufactured metal nanocrystals into the TiO2 matrix, significantly boosting carrier mobility.
• The proposed mechanism combines plasmonic-induced hot electron injection and enhanced conductivity from Schottky contact-derived oxygen vacancies, leading to improved photocharge separation and transport.
• The TiO2-based photocathode achieves benchmark performance in photoassisted lithium-ion batteries, including a capacity of 276 mAh g−1 at 0.2 A g−1 under illumination and a photoconversion efficiency of 1.276% at 3 A g−1.
• The bulk heterojunction strategy demonstrates excellent stability with minimal capacity and Coulombic efficiency loss over 200 cycles, highlighting its potential for efficient and stable photoassisted energy storage systems.