As　an　emerging　class　of　hybrid　complexes,　donor-acceptor　(D-A)　hybrid　heterostructures,　which　combine　the　advantages　of　both　organic　and　inorganic　photoactive　components,　provide　excellent　platforms　for　the　fabrication　of　photochromic　materials　with　enhanced　photo-responsive　performances.　Herein,　four　novel　hybrid　heterostructures,　namely　H3TPT·(PW12O40)·2NMP　(1),　(H1.5TPT)2·(PW12O40)　(2),　(H3TPT)2·(SiW12O40)·2Cl·2MeCN　(3),　and　H3TPT·(HPMo12O40)·Cl·3NMP　(4)　(TPT　is　tri(4-pyridyl)-s-triazine,　NMP　is　N-methylpyrrolidone),　have　been　synthesized　and　characterized.　Benefitting　from　the　strong　interactions　(anion-π　interactions)　and　matching　electron　energy　levels　between　the　donors　and　acceptors,　some　of　them　exhibited　ultrafast　photochromic　behaviour　even　up　to　1　second.　Furthermore,　based　on　experimental　and　theoretical　calculations,　the　plausible　PIET　process　and　structure-activity　relationship　have　been　discussed　in　detail.　©　2024　The　Royal　Society　of　Chemistry.