Abstract As an alternative strategy for H 2 production under ambient conditions, solar‐driven lignocellulose‐to‐H 2 conversion provides a very attractive approach to store and utilize solar energy sustainably. Exploiting efficient photocatalyst for photocatalytic lignocellulose‐to‐H 2 conversion is of huge significance and remains the key challenge for development of solar H 2 generation from lignocellulose. Herein, 2D‐2D MoS 2 /TiO 2 photocatalysts with large 2D nanojunction were constructed for photocatalytic lignocellulose‐to‐H 2 conversion. In this smart structure, the 2D nanojunctions acted as efficient channel for charge transfer from TiO 2 to MoS 2 to improve charge separation efficiency and thus enhance photocatalytic lignocellulose‐to‐H 2 conversion activity. The 2 % MoS 2 /TiO 2 photocatalyst showed the highest photocatalytic lignocellulose‐to‐H 2 conversion performance with the maximal H 2 generation rate of 201 and 21.4 μmol h −1 g −1 in α‐cellulose and poplar wood chip aqueous solution, respectively. The apparent quantum yield at 380 nm reached 1.45 % for 2 % 2D‐2D TiO 2 /MoS 2 photocatalyst in α‐cellulose aqueous solution. This work highlights the importance of optimizing the interface structures of photocatalyst for solar‐driven lignocellulose‐to‐H 2 conversion.