Two different poly(amic acid)s were synthesized by the polycondensations of 1-(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (CF3DAN) with p-phenylene diamine and benzidine. In addition, an amide acid model compound was prepared from CF3DAN and aniline. Isomeric units in the poly(amic acid)s as well as the amide acid were investigated by H-1 and C-13-nuclear magnetic resonance (NMR) spectroscopies. Spectroscopic results indicate that the major isomeric component was a CF3-meta-isomeric unit centered on the aromatic carbon substituted with the trifluoromethyl group. In particular, the amide acid compound was determined to be composed of 80 mol % CFS-meta-isomer and 20 mol % H-meta-isomer. Therefore, for the poly(amic acid)s, the minor isomeric component is speculated to be a H-meta-isomeric unit rather than a para-isomeric unit. The result might result mainly from the strong electron-withdrawable and bulky trifluoromethyl substituent in the CF3DAN monomer. The strong electron withdrawability might significantly enhance the reactivities of the adjacent carbons in the monomer to the nucleophilic attack of the amino nitrogen in the aniline and diamines, and consequently overcome the role of the bulkyness, ultimately leading to the amide acid and poly(amic acid)s rich with the CF3-meta-isomeric unit. In addition, a portion of the imide form was detected in the dried AN-CF3DAM-AN amide acid. Thus, the formation of imide linkage might be involved in a small portion for the dried poly(amic acid)s.