The　self-assembly　of　electron-deficient　protonated　N,　N′-dipyridyltetrachloroperylenediimide　(4Cl-DPPDI)　and　electron-rich　polyoxometalate　acids　HnXM12O40　(POMs;　X　=　P　or　Si;　M　=　W　or　Mo)　resulted　in　four　isomorphous　donor-acceptor　hybrid　crystals　1-4　with　segregated　POM　anions　and　one-dimensional　racemic　hydrogen-bonded　4Cl-DPPDI　networks　as　electron-donor　and-acceptor　components,　respectively.　Because　of　the　compact　contacts　between　the　POM　anions　and　4Cl-DPPDI　tectons　induced　by　anion-πinteractions,　besides　enhanced　photochromism,　these　four　unique　isostructural　hybrids　exhibited　unusual　room-temperature　phosphorescence　(RTP)　emissions.　More　interestingly,　owing　to　the　facial　compact　contacts　of　two　racemic　4Cl-DPPDI　tectons　induced　by　lone　pair-π-assisted　π-πinteractions,　they　also　showed　unprecedented　photon　upconversion　by　triplet-triplet　annihilation　(TTA).　©　2021　American　Chemical　Society.