We evaluate the potential of microporous coordination polymers (MCPs) to act as the stationary phase in liquid chromatographic separations. MCPs derived from carboxylates coordinated to copper (HKUST-1) and zinc (MOF-5) were studied. The shape and size selective separation of organic compounds including benzene, ethylbenzene, styrene, naphthalene, anthracene, phenanthrene, pyrene, 1,3,5-triphenylbenzene, and 1,3,5-tris(4-bromophenyl)benzene was performed, and in most cases excellent separation was achieved based on a combination of molecular sieving and adsorption effects.