Alternating copolymers derived from the ring-opening metathesis polymerization (ROMP) of functionalized cyclobutene esters (CBE) and cyclohexenes (CH) are described. The copolymer poly(CBE-alt-CH)n contains alternating side-chains based on dialcoxynaphthalene (DAN) and pyromellitc dianhydride (PDI). Characterization by UV-Vis spectroscopy showed that the copolymers exhibit an increase in charge-transfer intensity in comparison to previously reported alternating copolymers. The bulky side-chains inhibit backbiting during the polymerization and allow for enhanced control over the polymerization in comparison to copolymers functionalized with linear alkyl groups.