Donor-acceptor　(D-A)　hybrid　heterostructures　are　an　emerging　class　of　hybrid　complexes　with　potential　applications　in　current　optoelectronic　technologies.　To　achieve　high　photoinduced　charge-carrier　generation　and　separation　in　a　heterostructure,　a　common　strategy　is　the　fabrication　of　continuous　or　bicontinuous　structures　by　the　crystallization　of　semiconductive　donor　and　acceptor　tectons　at　the　molecular　level.　So　far,　only　a　few　such　heterostructures　have　been　fabricated,　most　of　which　involve　unstable　and　narrow　band　gap　metal　halides.　In　this　paper,　we　extended　these　unique　hybrid　heterostructures　to　continuous　alkaline-earth　metal　oxide　clusters.　The　combination　of　the　naphthalene　diimide　(NDI)　tecton　bearing　four　carboxylates　at　two　extremities　with　Ca2+　(or　Sr2+)　cations　led　to　two　isostructural　D-A　hybrid　heterostructures　with　infinite　1-D　carbon-doped　alkaline-earth　metal　oxide　clusters　and　X-aggregated　NDI　dimers　as　electron　donors　and　acceptors,　respectively.　Due　to　the　different　metal　cations　in　inorganic　clusters,　they　exhibited　diametrically　opposite　photochromic　sensitivities　and　photocatalytic　activities.　To　better　rationalize　them,　a　plausible　photoinduced　electron　transfer　process　for　the　D-A　hybrid　heterostructures　with　photoactive　acceptors　has　been　developed.　This　journal　is　©　The　Royal　Society　of　Chemistry.