Donor-acceptor　(D-A)　hybrid　heterostructures,　an　emerging　class　of　crystalline　hybrid　complexes　composed　of　semiconducting　organic　and　inorganic　components,　have　attracted　much　attention　as　photochromic　materials.　Among　them,　photochromic　polyoxometalate/naphthalenediimide　D-A　hybrid　heterostructures　represent　the　most　investigated　ones,　whose　photochromic　properties　are　strongly　dependent　on　the　structures　of　polyoxometalates　and　naphthalenediimides.　Herein,　we　reported　their　photochromic　properties　are　controlled　by　their　moculelar　packings,　which　were　achieved　by　their　diffusion　methods.　Eight　polyoxometalate/naphthalenediimide　D-A　hybrid　heterostructures　have　been　synthesized　by　the　combinations　of　metal　salts　(ZnSiF6·6H2O　or　Zn(ClO4)2·6H2O),　heteropoly　acid　(H3PMo12O40　or　H3PW12O40)　and　N,N-di　(4-pyridyl)-1,4,5,8-naphthalene　diimide　(DPNDI)　via　two　diffusion　methods　(A　and　B).　Interestingly,　single-crystal　X-ray　diffraction　analyses　reveal　that　they　belong　to　three　categories　of　isostructures　with　layered,　sandwich　and　interpenetrating　packing　patterns.　Their　photochromic　properties　have　been　carefully　investigated,　and　the　impacts　of　polyoxometalates　as　well　as　packing　patterns　have　also　been　discussed.　©　2020　Elsevier　Ltd