Different　combinations　of　donors　and　acceptors　of　charge　transfer　complexes　(CTCs)　can　realize　visible　light　catalysis　in　multiple　wavelength　bands.　Here,　we　successfully　demonstrated　that　2-bromoacetophenone　as　an　electron　acceptor,　combined　with　amines　(for　formation　of　CTC),　can　achieve　photopolymerization　under　LED@405　nm　visible　light　irradiation,　initiating　the　polymerization　of　(meth)acrylates,　and　the　induction　time　can　be　completely　eliminated　by　condition　optimization.　The　CTC　was　also　shown　to　have　dual　photo/thermal　initiation　capability　and　was　eventually　applied　to　3D　printing　as　well.　©　2023　The　Authors.　Journal　of　Polymer　Science　published　by　Wiley　Periodicals　LLC.