Chromatographic separations of synthetic and natural polymers are usually affected by a size exclusion chromatography (SEC) mechanism. Although SEC is a proven method of separation based on hydrodynamic size, a chromatographic method based solely on chemical interactions would present certain advantages. This laboratory has been investigating the use of capillary-channeled polymer (C-CP) fibers as stationary phases in HPLC for the separation of biomacromolecules. C-CP fibers allow highly efficient fluid transport and an amorphous surface structure, minimizing mass transfer effects commonly associated with porous, packed-bed technologies. Choice of the base fiber identity allows flexibility in the potential types of solute-surface interactions. Two water-soluble polymers, glycolic acid ethoxylate 4-nonylphenyl ether, and poly(4-vinylpyridine hydrochloride), were used as test solutes because of their similarities to polymers of interest in the consumer products industry. SEC separation of this pair was not possible due to the similarities in hydrodynamic size. Poly(ethylene terephthalate), polyester and nylon-6 C-CP fibers were evaluated as stationary phase materials. The former was found to offer superior chromatographic separations and recoveries when operating under what would be considered to be typical RP separation conditions: a flow rate of 1 mL/min and gradient of 0-100% H(2)O/ACN with 0.06% TFA over 5 min.