A series of novel biselectrophilic β,γ-unsaturated α-ketoesters were designed and synthesized from rhodanine. Under the catalysis of chiral squaramides, the enantioselective [3 + 3] annulation reaction of these novel ketoesters with pyrazolones was developed. This reaction offers an efficient method for the synthesis of chiral 2'-thioxo-5,6-dihydrospiro[pyrano[2,3-c]pyrazole-4,5'-thiazolidin]-4'-ones.