Metal-free　carbon-based　hybrids　composed　of　reduced　graphene　oxide　(rGO)　and　C3N3S3　polymers　with　a　layered　＂sandwich＂　structure　were　fabricated　by　an　in　situ　two-step　polymerization　strategy　and　used　as　visible　light　photocatalysts　for　selective　aerobic　oxygenation　of　benzylic　alcohols　to　the　corresponding　aldehydes,　at　good　efficiency　and　high　selectivity.　This　work　shows　the　great　potential　and　prospective　application　of　the　metal-free　C3N3S3　polymer　in　the　photocatalyzed　synthesis　of　fine　chemicals.