The reaction of a rhodanine derivative (= (Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyl-oxirane (2) in the presence of SiO2 in dry CH2Cl2 for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (C=S) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO2-activated oxirane ring proceeds with high regio- and stereoselectivity via an SN2-type mechanism.