Ternary　NiTiFe-LDH　with　an　ultrathin　nanosheet　morphology　was　successfully　fabricated　via　a　facile　co-precipitation　method,　followed　by　refluxing,　and　was　used　as　a　catalyst　for　oxidative　coupling　of　amines　to　produce　imines　under　visible　light.　The　obvious　superior　activity　observed　in　NiTiFe-LDH　ultrathin　nanosheets　compared　with　binary　NiTi-LDH　and　bulk　NiTiFe-LDH　can　be　ascribed　to　an　enhanced　light　absorption　capability　caused　by　the　introduction　of　Fe3+　ions　as　well　as　the　ultrathin　nanosheets　which　can　minimize　the　recombination　of　the　photogenerated　charge　carriers　and　provide　more　catalytically　active　sites　for　the　reaction.　As　a　result,　more　catalytically　active　O2˙−　radicals　are　generated　over　NiTiFe-LDH　ultrathin　nanosheets,　which　leads　to　their　superior　activity.　This　study　not　only　shows　the　possibility　of　using　LDHs　in　photocatalytic　organic　transformations　but　also　demonstrates　an　effective　strategy　to　promote　the　activity　of　LDH-based　photocatalysts　via　simultaneous　composition　and　morphology　modulation　of　LDHs.　©　2024　The　Royal　Society　of　Chemistry.