Photocatalysis is a potentially promising approach to harvest aromatic compounds from lignin. However, the development of an active and selective solid photocatalyst is still challenging for lignin transformation under ambient conditions. We herein report a mild photocatalytic oxidative strategy for C–C bond cleavage of lignin β-O-4 and β-1 linkages using a mesoporous graphitic carbon nitride catalyst. Identifications by solid-state NMR techniques and density functional theory (DFT) calculations indicate that π–π stacking interactions are most likely present between the flexible carbon nitride surface and lignin model molecule. Besides, low charge recombination efficiency and high specific surface area (206.5 m2 g–1) of the catalyst also contribute to its high catalytic activity. Mechanistic investigations reveal that photogenerated holes, as the main active species, trigger the oxidation and C–C bond cleavage of lignin models. This study sheds light on the interaction between complex lignin structures and the catalyst surface and provides a new strategy of photocatalytic cleavage of lignin models with heterogeneous photocatalysts.