Cyclic peptides are valued synthetic targets in organic and medicinal chemistry. Herein, we report an efficient strategy for the synthesis of unnatural cyclic peptides via the Cu-catalyzed 1,3-dipolar cycloaddition of azomethylene ylides. Linear precursors of different lengths and bearing diverse amino acids (26 examples) are shown to be compatible with this method, affording good yields and complete endo-diastereoselectivities. Density functional theory (DFT) calculations support a stepwise mechanism in which Cu plays a key role in the preorganization of the reactants.