The synthesis of analogs of tetra‐l‐alanine containing 3‐fluoro‐l‐alanine selectively incorporated at each position is described. The standard procedures in the literature used to couplel‐alanine peptides together were often found to lead to undesired products, or elimination reactions when corresponding 3‐fluoro‐l‐alanine peptide analogs were used. Several modified procedures have thus been developed for the synthesis of fluorine‐substituted analogs. In addition, the pH‐dependence of19F n.m.r. spectra of 3‐fluoro‐l‐alanine and the tetrap