An organic soluble polyimide was prepared from 3,3â ²-dihydroxybenzidine and 2,2-bis(phthalic anhydride)hexafluoropropane. The two hydroxy groups in the repeating unit of the polyimide thus prepared were utilized in attaching 4-nitro-4â ²-diphenylaminoazobenzene chromophores onto the main chain perpendicularly (or in an end-on fashion) or laterally (or in a side-on fashion) through either the oxydimethylene or oxyhexamethylene spacer. All the polymers revealed two strong absorptions: one λmax at 300â nm and the other λmax at 493â nm. The polymers, when electrically poled, showed 2^nd order nonlinear optical properties, r33â =â 9â 23â pmâ V^{â 1} at 1300â nm, r33â =â 102â 194â pmâ V^{â 1} at 633â nm, and d33â =â 59â 109â pmâ V^{â 1} at 1064â nm depending on their structure. The polymers bearing side-on attached chromophores revealed higher r33 values than those with end-on attached chromophores. Temporal stability of the former was also greater than that of the latter.