Poly(imide p-alkoxycinnamate)s of various alkyl chain lengths were synthesized by esterifying chloromethylated polyimide (CMPI), a synthetic platform for functionalized polyimides. Soluble CMPI, obtained by chloromethylation of soluble polyimide from diaminodiphenylether and 4,4’-(hexafluoroisopropylidene) diphthalic anhydride, was esterified with various p-alkoxycinnamic acids in the presence of base and phase transfer catalyst. The reaction underwent almost quantitatively. The structure of resulting polymer was characterized by 1H-NMR and FT-IR spectroscopic methods. Thin polymer film on a glass substrate was irradiated with polarized UV light, inducing a homogeneous liquid crystal alignment.