Acylation of halogen-containing electron-rich aromatic and heteroaromatic compounds with β-ethylsulfanylpropionyl tetrafluoroborate leads to the formation of 6-membered sulfonium salts fused with aromatic or heteroaromatic rings. Base induced cleavage of sulfonium salts gave ethylsulfanyl substituted aryl vinyl ketones. Cyclic sulfonium salts can also be converted into corresponding thiopyran-4-ones by treatment with thiourea in MeOH.