How the characteristics and stability of the rubbing-induced alignment of nematic liquid crystals (LCs) relate to the interfacial characteristics of LC-polyimide has been studied. The characteristics of the LC alignment (such as the LC texture, the pretilt angle, and the anchoring energy) and their thermal stability have been investigated for 5 polyimides synthesized for this work. The work showed that the rubbed polyimide alignment layer induces the strong LC anchoring and that the characteristics and stability of LC alignment are determined by the short-ranged interactions between LC and polyimide molecules at the alignment layer surface. The increased flexibility of the polyimide accelerates thermal imidization, increases the pretilt angle, and improves the alignment stability. It also turned out that fluorination of the polyimide tends to deteriorate the alignment uniformity and stability. No distinct differences in the alignment characteristics were shown for the aromatic- and alicyclic-dianhydride polyimides.