The dehydrogenation and conversion of methanol into 1,1-dimethoxymethane (DMM) was achieved over noble metal-free photocatalyst CdS/Ni₂P under visible light. This photocatalytic process for methanol-to-H₂ and DMM conversion is efficient and atom economic, with an optimal rate and selectivity of DMM of 188.42 mmol g⁻¹ h⁻¹ and 82.93%, respectively. This work supplies a new green approach for the direct efficient conversion of methanol into DMM and provides a promising avenue for sustainable bio-methanol applications.