Epitaxial growth of the perfectly alternating ethylene-carbon monoxide copolymer (POK) has been successfully achieved using hydroquinone, first as a solvent in its liquid state, and then as a substrate in its crystallized form. Mono-oriented POK domains grow directly in the alpha crystal form. The polymer chain axis lies parallel to the substrate surface and each domain is composed of a stack of lamellae standing edgewise; the contact plane with the substrate is the crystallographically dense (100) plane.