Visible　light　induced　oxidative　C-C　and　C-N　coupling　provides　a　milder　alternative　to　the　current　synthetic　strategies.　However,　the　photochemical　C-C　coupling　of　benzylamine　and　chromoselective　C-C/C-N　conversion　are　not　widely　reported.　Herein,　we　demonstrate　that　the　introduction　of　indium　vacancies　in　ZnIn2S4　improves　the　catalytic　activity　for　C-C　coupling　of　benzylamine　and　imparts　a　strong　chromoselectivity　for　C-C　or　C-N　coupled　products.　A　high　C-C　selectivity　of　similar　to　80%　is　achieved　with　a　benzylamine　conversion　of　similar　to　80%.　Mechanistic　studies　unveil　the　switchable　reaction　routes　between　kinetically　favored　C-C　coupling　and　thermodynamically　favored　C-N　coupling　under　specific　illumination　conditions.