As　an　emerging　class　of　hybrid　materials,　donor-acceptor　(D-A)　hybrid　crystals　with　photoactive　organic　and　inorganic　components　have　gradually　become　an　ideal　platform　for　photochromic　materials.　Wherein　the　most　available　organic　components　are　electron-poor　naphthalenediimide,　pyridinium,　and　triazine　derivatives,　inorganic　units　are　electron-rich　polyoxometalates　and　metal　halides.　Herein,　we　introduced　pyridinium　moieties　into　the　naphthalenediimide　core　by　conjugated　bonds　so　as　to　increase　the　electron　deficiency　of　organic　species　for　enhanced　photochromic　properties.　Four　anion-π　interaction　directed　hybrid　crystals,　(Me2DPNDI)3·(PW12O40)2　(1),　(Et2DPNDI)3·(DMSO)2·(PMo12O40)2　(2),　(Et2DPNDI)3·(PW12O40)2　(3),　and　(Et2DPNDI)2·(SiMo12O40)　(4),　have　been　obtained,　which　possess　reversible,　naked-eye　perceptible　color　changes　with　varying　light　response　rates.　These　rates　are　as　follows:　3　＞　1　＞　4　＞　2.　As　expected,　such　D-A　hybrid　crystals　with　conjugated　naphthalenediimide-pyridinium　salts　feature　both　photo-　and　thermally　induced　electron　transfer　pathways,　along　with　enhanced　anion-π　interactions.　Consequently,　they　demonstrate　a　higher　rate　of　photochromism　compared　to　those　of　hybrids　containing　naphthalenediimide　or　pyridinium　derivatives　as　organic　acceptors.　©　2024　American　Chemical　Society.