Poly(ethylene naphthalate) (PEN) copolymers were prepared by melt polycondensation of dimethyl naphthalate and excess ethylene glycol with 5-40 mol % (in feed) of 1,3-propanediol or 2,2-dialkyl-1,3-propanediols, where the dialkyl groups are dimethyl, diethyl, and butyl-ethyl. No significant depression of reduced specific viscosity was observed. The comonomer contents in the copolymers are considerably higher than those in the feed. The effects of the copolymer composition on the structures of the films were investigated using thermal analyses, density measurements, X-ray diffraction methods, and other physical tests. The crystallinities and densities of heat-treated films decreased with increasing content of comonomer and length of alkyl side chain in the comonomer. The glass transition temperature (T g ) and melting temperature (T m ) were decreased by the copolymerization, while an increase in the length of the alkyl side chain hardly affected T m s of the heat-treated films. Alkali resistance, moisture resistance, dye ability, and thermal shrinkage were increased by the incorporation of comonomer having an alkyl side chain.