Avoparcin is a macrocyclic glycopeptide antibiotic structurally related to vancomycin, teicoplanin, and ristocetin A. When attached to 5‐μm spherical silica gel, the avoparcin proved to be an effective chiral stationary phase (CSP) that could be used in the reversed‐phase, normal‐phase, and polar‐organic modes. The avoparcin CSP was complimentary to the other macrocyclic glycopeptide CSPs in that it could resolve some racemates that the others could not, and vice versa. Some important compounds resolved on the avoparcin CSP include verapamil, thyroxine, mephenytoin, and 2‐imidazolidone‐4‐carboxylic acid. The use of this CSP and the optimization of separations on it are discussed. Avoparcin appears to be a useful addition to this family of CSPs. Chirality 10:627–660, 1998. © 1998 Wiley‐Liss, Inc.