Cellulose continues to play an important and emerging role in photocatalysis, and its favourable properties, such as electron-rich hydroxyl groups, could enhance the performance of photocatalytic reactions. For the first time, this study exploited the kapok fibre with microtubular structure (t-KF) as a solid electron donor to enhance the photocatalytic activity of C-doped g-C3N4 (CCN) via ligand-to-metal-charge-transfer (LMCT) to improve hydrogen peroxide (H2O2) production performance. As confirmed by various characterisation techniques, the hybrid complex consisting of CCN grafted on t-KF was successfully developed in the presence of succinic acid (SA) as a cross-linker via a simple hydrothermal approach. The complexation formation between CCN and t-KF results in the CCN-SA/t-KF sample displaying a higher photocatalytic activity than pristine g-C3N4 to produce H2O2 under visible light irradiation. The enhanced physicochemical and optoelectronic properties of CCN-SA/t-KF imply that the LMCT mechanism is crucial in improving photocatalytic activity. This study promotes utilising the unique t-KF material's properties to develop a low-cost and high-performance cellulose-based LMCT photocatalyst.