Zweifel　reaction　is　a　powerful　strategy　to　construct　olefins　from　alkenyl　tetracoordinate　borons　in　organoboron　chemistry,　however,　it　usually　only　involves　one　functional　group　migration　and　then　undergoes　an　elimination　process　affording　alkenes　or　alkynes　exclusively.　Herein,　we　disclose　several　intriguing　interception　of　alkynyl　tetracoordinate　borons　with　sulfur　electrophiles.　Wherein,　the　substituted　benzothiophenes　are　accessed　by　consecutive　1,2-migrations　and　intramolecular　electrophilic　substitution,　meanwhile,　the　challenging　and　elusive　five/four-membered　boracycles　are　easily　assembled,　and　an　approach　to　alkenyl　sulfides　with　good　stereoselectivity　was　developed　as　well.　Moreover,　by　adding　readily　available　deuterium　sources,　the　tetrasubstituted　deuterated　alkenyl　sulfides　with　high　deuteration　rates　are　constructed.　These　protocols　not　only　improve　atom　economy　by　prohibiting　the　elimination　of　Zweifel　intermediate,　but　also　enrich　the　reaction　modes　of　alkynyl　tetracoordinate　borons　achieving　versatile　value-added　sulfur-containing　molecules.　Mechanistic　investigations　illustrate　that　dichlorosulfoxide　(SOCl2)　and　dialkylaminosulfur　trifluoride-type　reagents　(DAST-type)　as　surfur　sources　could　promote　dual　1,2-aryl　migration　of　alkynyl　tetracoordinate　borons,　which　are　distinct　from　traditional　Zweifel　reaction,　and　the　regulation　of　steric　hindrance　could　also　make　four-membered　boracycles　and　alkenyl　sulfides　feasible.　And　these　transformations　feature　novel　reaction　modes　and　unusual　reaction　mechanisms　with　valuable　products　in　high　efficiency.　©　2024　Wiley-VCH　GmbH.