The solid-phase synthesis of Gly-Ψ[CH(CF 3 )NH]-peptides is presented. In order to achieve this goal, the synthesis of Gly-Ψ[CH(CF 3 )NH]-dipeptides having the C-terminus unprotected, the N-terminus protected as Fmoc- or Teoc-, and possibly side chain functionalities protected with acid-labile protecting groups has been developed. A selected small library of six peptidomimetics, encompassing analogues of biological relevant peptides, have been obtained in high purity.