A short and convenient synthesis for four novel chiral L-proline derived macrocyclic dioxopolyamines of C-2 symmetry, by condensation of appropriate diester intermediates and polyamines, is reported. These macrocyclic dioxopolyamines may be applied as chiral solvating agents for enantiomeric recognition, and the work also provided a simple and convenient way for the synthesis of the diester intermediates.