A strongly coupled mesoporous SnO₂–graphene hybrid has been prepared via direct nucleation, growth, and anchoring of a SnO₂ nanocrystal on graphene substrate under microwave irradiation followed by heat-treatment. Investigations reveal that the well-dispersed SnO₂ nanocrystals with a uniform particle size of 3–5 nm are homogeneously distributed on the surface of graphene through strong chemical attachment and electrical interaction. The formed structure exhibits a high specific surface area (280.7 m² g⁻¹) and an ideal synergistic effect, which can provide improved activity and durability for the electrochemical and photocatalytic reaction. Lithium-ion battery performance and photocatalytic activity of the resultant mesoporous SnO₂–graphene hybrid are thoroughly investigated. In comparison to bare SnO₂ nanoparticles, the hybrid shows substantial enhancement in electrochemical lithium storage properties and photocatalytic hydrogen evolution. More strikingly, the as-synthesized SnO₂–graphene hybrid anode could deliver initial discharge and charge capacities of 2445.7 and 1329.4 mAh g⁻¹ with a high initial Coulombic efficiency (54.4%), as well as an excellent cycling stability.