Herein, an environmentally friendly CoP/Zn2In2S5 catalyst is reported as a visible-light photocatalyst for the selective activation of the α-C-H bond of methanol to generate ethylene glycol with a selectivity of as high as 90%. The catalytic system also illustrates the first example of visible-light-driven dehydrogenative coupling of ethanol to 2,3-butanediol.