An　atomically　economical　green　protocol　for　the　hydrofunctionalization　of　olefins　to　higher　aliphatic　alcohols　with　100%　anti-Markovnikov　regioselectivity　was　developed　via　visible-light　photocatalytic　coupling.　This　method　employs　cheap,　readily　available　and　abundant　methanol　as　both　the　C1　feedstock　and　the　hydrogen　source　under　visible　light　irradiation　over　CdS　photocatalyst.　A　wide　scope　of　olefin　substrates　could　be　hydrofunctionalized　successfully　to　the　corresponding　higher　alcohols　with　high　selectivity.　Besides　alcohol,　acetone　and　acetonitrile　can　also　couple　with　olefins　to　generate　the　corresponding　hydrofunctionalization　products,　suggesting　promising　potential　industrial　application.　[GRAPHICS]　.