An efficient method for diastereo-controlled synthesis of (Z)-fluoroalkene dipeptide isosteres (FADIs) was developed. Two chiral centers were constructed by applying our synthetic methodology for chloroalkene dipeptide isosteres (CADIs) using Ellman's imine for corresponding to the N-terminal amino acid residues and Oppolzer's sultam for corresponding to the C-terminal amino acid residues, affording dipeptidomimetic in a stereocontrolled manner with high diastereoselectivity.