[2　+　2　+　2]　Cycloaddition　reactions　have　emerged　as　one　of　the　most　powerful　approaches　for　constructing　highly　substituted　six-membered　rings.　However,　enantioselective　[2　+　2　+　2]　cycloadditions　catalyzed　by　transition　metal　catalysts　and　chiral　ligands　are　often　limited　by　narrow　substrate　scopes　and　insufficient　catalyst/ligand　diversity.　In　this　study,　we　employ　an　innovative　Si-centered　spirodiphosphine　(Si-SDP)　ligand　that　enables　Rh-catalyzed　asymmetric　[2　+　2　+　2]　cycloadditions　of　1,6-diynes　with　2π-components;　this　achieves　high　yields　and　enantioselectivities　(up　to　99%　ee).　The　Rh/Si-SDP　catalyst　has　broad　substrate　versatility　and　functional　group　tolerance　and　enables　the　synthesis　of　more　than　60　examples　of　cyclohexadienes　bearing　chiral　centers　with　carbon　or　nitrogen　substituents.　The　incorporation　of　silicon　at　the　center　of　the　spirodiphosphine　ligand　is　crucial　for　high　catalytic　activity　and　stereoselectivity.　This　work　highlights　the　potential　of　the　Rh/Si-SDP　catalytic　system　for　synthesizing　complex　chiral　molecules　and　addresses　the　challenging　problems　in　asymmetric　catalysis.　©　2025　American　Chemical　Society.