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A green and efficient method for the construction of functionalized 2,3-dihydrothiophene derivatives in water was reported. In this work, Novozym 435 acted as a remarkable biocatalyst in catalyzing the four-component reaction of aldehydes, malonitrile or ethyl cyanoacetate, 1,3-thiazolidinedione, and amines under mild conditions. Excellent yields (85–95%) of all the corresponding products could be obtained in reasonable reaction time. Moreover, Novozym 435 could be reused for six cycles with a yield of at least 80%. The rationality of this multicomponent reaction mechanism was also verified via control experiments. [ABSTRACT FROM AUTHOR]