The　photocycloaddition　of　1,4-dihydropyridines　(1,4-DHPs)is　amain　approach　to　synthesize　structurally　complex　compounds,　whichare　important　intermediates　for　the　preparation　of　cage　compounds,such　as　3,9-diazatetraasterane,　3,6-diazatetraasterane,　3,9-diazatetracyclododecane,and　6,12-diazaterakishomocubanes.　The　acquisition　of　different　cagecompounds　depended　on　the　chemoselectivity,　which　is　mainly　causedby　the　reaction　conditions　and　structural　characteristics　of　1,4-DHPs.This　study　aimed　to　investigate　the　effect　of　the　structural　characteristicson　chemoselectivity　in　[2　+　2]/[3　+　2]　photocycloaddition　of　1,4-DHPs.The　photocycloadditions　were　conducted　on　the　1,4-diaryl-1,4-dihydropyridine-3-carboxylicester　with　steric　hindrance　groups　at　the　C3　position　or　chiralityat　the　C4　position　irradiated　by　a　430　nm　blue　LED　lamp.　When　the1,4-DHPs　contained　high　steric　hindrance　groups　at　the　C3　position,[2　+　2]　photocycloaddition　was　the　main　reaction,　resulting　in　3,9-diazatetraasteraneswith　a　yield　of　57%.　Conversely,　when　the　1,4-DHPs　were　resolved　toa　chiral　isomer,　the　main　reaction　was　[3　+　2]　photocycloaddition,producing　6,12-diazaterakishomocubanes　with　a　yield　of　87%.　To　investigatethe　chemoselectivity　and　understand　the　photocycloaddition　of　1,4-DHPs,density　functional　theory　(DFT)　and　time-dependent　DFT　(TDDFT)　calculationswere　performed　at　the　B3LYP-D3/def-SVP//M06-2X-D3/def2-TZVP　level.The　steric　hindrance　and　excitation　energy　modulated　by　substituentsat　the　C3　position　and　chiral　carbon　at　the　C4　position　were　crucialfor　the　chemoselectivity　in　[2　+　2]/[3　+　2]　photocycloaddition　of1,4-DHPs.