Abstract: The first thiourea-catalyzed addition reaction of indoles to aliphatic β,γ-unsaturated α-ketoesters has been developed. The easily accessible thiourea aminoindanol derivative makes this approach an interesting alternative for these aliphatic substrates, very scarcely employed in previously reported procedures, highlighting the complementarity of the strategy presented here. Final adducts, which are valuable intermediates for the obtainment of the corresponding α-amino acid or α-hydroxy acid derivatives, are obtained in good results under mild reaction conditions.