Polyimides(PI) with different side chains in structure were synthesized by copolycondensation of pyromelliticmdianhydride(PMDA) with 3,5-diamino-(4’-methane acid hexyl ester) phenyl-benzamide(C6-PDA),(4-butoxybiphenol)-3’, 5’-diaminobenzoate(C4-BBDA) and 3, 5-diamino-benzoic acid decyl ester(C10-DA) named PI-PDA, PI-C4, PI-DA, respectively. The lengths of side chains of PI-PDA and PI-DA are as similar as that of PI-C4. Through the pretilt angle tests it is demonstrated that neither the structure of side chains nor the rubbing process could make an obvious difference on vertical alignment property when the lengths of the side chains are similar, standing at around 1.6 nm. The measurement of surface energy of PI surfaces further proved this result. The result of the X-ray photo-electron spectroscope measurement indicated that the side chains of PIs stretched out from the polymer bulk phase and accumulated on the surface. Polyimides (PI) with different side chains in the structure were synthesized by copolycondensation of pyromelliticmdianhydride (PMDA) with 3,5-diamino- (4’-methane acid hexyl ester) phenyl- benzamide (C6- PDA), (4-butoxybiphenol) 3 ’, 5’-diaminobenzoate (C4-BBDA) and 3, 5-diamino-benzoic acid decyl ester (C10-DA) named PI- PDA, PI- C4, PI- DA, respectively. The lengths of side chains of PI -PDA and PI-DA are as similar as that of PI-C4. Through the pretilt angle tests it is said that neither the structure of side chains nor the rubbing process could make an obvious difference on vertical alignment property when the lengths of the side The results of the X-ray photo-electron spectroscope measurement that the side chains of PIs stretched out from the polymer bulk phase and accumulated on the surface