Flowerlike　nanospheres　of　ZnIn2S4　consisting　of　interweaving　nanoflakes　were　prepared　by　a　rapid　microwave-assisted　solvothermal　method.　The　photocatalytic　performance　of　ZnIn2S4　in　the　aerobic　oxidation　of　amines　to　imines　is　for　the　first　time　revealed.　As-prepared　ZnIn2S4　showed　high　efficiency　for　the　transformations　of　various　amines　into　their　corresponding　imines　under　visible-light　irradiation　by　using　air　as　the　oxidant.　The　photocatalytic　performance　of　ZnIn2S4　in　the　selective　oxidation　of　amines　to　their　corresponding　imines　is　much　higher　than　that　of　graphitic　C3N4　and　CdS　previously　reported.　A　plausible　mechanism　involving　the　oxygenation　of　amines　to　form　aldehydes,　followed　by　the　nucleophilic　addition　of　the　amines　to　afford　the　final　imines　is　proposed.　The　use　of　a　cheap,　environmentally　friendly　inorganic　semiconductor　photocatalyst　and　solar　energy　makes　this　transformation　green　and　sustainable.　©　2014　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.