Room-temperature　phosphorescence　(RTP)　has　attracted　much　attention　in　the　past　decades　due　to　its　potential　applications　in　optoelectronic　devices　and　bioimaging.　So　far,　most　available　RTP　materials　are　pure　inorganic　or　organic　compounds,　few　are　involved　in　the　organic-inorganic　hybrid　complexes.　The　donor-acceptor　(D-A)　hybrid　heterostructures　are　an　emerging　class　of　organic-inorganic　hybrid　complexes　composed　of　semiconductive　organic　and　inorganic　tectons　at　the　molecular　level.　For　these　unique　hybrids,　the　primary　properties　are　photochromism　and　photoinduced　electron　transfers.　Herein,　we　have　demonstrated　that　the　combination　of　naphthalene　diimide　(NDI)　tectons　bearing　two　divergently　oriented　pyridyl　protons　with　three　polyoxometalate　(POM)　anions　(SiW12O404−,　PW12O403−　or　PMo12O403−)　resulted　in　three　isostructural　D-A　hybrid　heterostructures　with　an　alternate　arrangement　of　segregated　POM　anions　and　1-D　H-bonded　NDI　networks　as　electron　donors　and　acceptors,　respectively.　Due　to　the　compact　contacts　between　POM　anions　and　NDI　tectons　induced　by　charge-assisted　anion-π　interactions,　not　only　the　photochromic　speeds　of　three　D-A　hybrid　heterostructures　have　been　enhanced,　but　more　interestingly　their　RTP　emissions　of　have　also　been　switched　on,　and　their　photoluminescence　quantum　yields　are　dependent　on　anion-π　interaction　strengths.　©　2019　Elsevier　Ltd