Conventional　photocycloaddition　of　1,4-dihydropyridines　does　not　afford　novel　head-to-head　3,6-diazatetraasteranes.　Herein,　we　describe　a　highly　regioselective　method　to　synthesize　3,6-diazatetraasteranes　via　an　intramolecular　photodimerization　of　1,4-dihydropyridines.　First,　the　1,4-dihydropyridines　were　tethered　by　phthaloyl　to　direct　a　proximate　parallel　arrangement　in　head-to　head　orientation　by　the　rotation　of　C-C　single　bonds　in　solution.　An　intramolecular　[2　+　2]　photocycloaddition　proceeded　subsequently　to　give　desired　3,6-diazatetraasteranes　in　high　yield　(92-97%)　and　excellent　regioselectivity.　Furthermore,　two　different　1,4-dihydropyridines　can　also　be　regiocontrolled　by　this　strategy　and　produce　polysubstituted　3,6-diazatetraasteranes　via　a　cross-photodimerization　in　a　concise　and　efficient　way.　In　addition,　this　approach　can　provide　direct　access　to　other　polysubstituted　polyhedron　scaffolds　from　1,4-dihydropyridine　analogues.　(C)　2017　Elsevier　Ltd.　All　rights　reserved.