A method for the synthesis of α,α-bisthiofunctionalized butenolide compounds has been successfully developed. The bis-sulfenylation of γ-substituted butenolides at α-position is promoted by using triethylamine as the catalyst and N-(aryl(alkyl)sulfanyl)succinimides or N-(phenylsulfanyl)phthalimides as sulfenylating reagents under mild reaction conditions. A range of α-sulfenylated butenolide derivatives could be smoothly obtained in moderate to excellent yields. A preliminary attempt at the catalytic asymmetric α-sulfenylation of α-methyl-γ-phenyl-substituted butenolide was also conducted and afforded promising enantioselectivity.