By　incorporating　a　viologen　moiety　into　a　framework,　a　multiresponsive　2D　bilayered　luminescent　Cd–viologen　complex　{[Cd1.5(Cebpy)(Hbtc)Cl]⋅H2O}n,　(1,　Cebpy=1-carboxyethyl-4,　4’-bipyridine,　H3Hbtc=1,　3,　5-benzenetricarboxylic　acid)　has　been　synthesized.　The　reversible　photochromism　from　light　brown　to　dark　bluish-grey　is　implemented　due　to　the　favourable　spatial　stack　of　the　electron　donor　and　acceptor.　The　photochromic　component　of　the　organic　linkers　can　modulate　the　luminescence　of　compound　1　under　irradiation　by　using　a　Xenon　lamp.　At　the　same　time,　compound　1　shows　a　good　potential　in　luminescent　sensing　for　colored　transition　metal　cations.　Thus,　multiphotofunctionality,　viz.　photoluminescence,　photochromism　as　well　as　the　derivate　fluorescent　responses　to　irradiation　and　colored　transition　metal　cations　have　been　combined　in　the　Cd–viologen　complex　1,　which　is　the　first　example　in　the　Cd–viologen-based　photochromic　hybrid　materials.　©　2018　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim