Heterocycle-braced cyclic peptides have demonstrated enhanced metabolic stability, increased potency and selectivity. Here, we present a rapid synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides with potent anti-proliferative activities against cancer cells, through C-H alkenylation and macrolactamization. This report addresses critical challenges associated with the installation and removal of the directing group N-Piv, configuration selectivity of the olefin, and intramolecular cyclization. Notably, this method exhibits mild reaction conditions, traceless removal of the directing group, and high configuration selectivity. Special E-configuration Trp-alkene crosslinks can be constructed at various linear peptides utilizing air-stable Rh(III) catalyst. In addition, an efficient synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides was developed, and this method demonstrates several advantages, including mild reaction conditions, traceless removal of the directing group, and specific configuration selectivity. Display omitted