A novel functional diamine containing triphenylamine moiety and biphenyl as well as a long alkyl chain, 4-dodecyloxy-biphenyl-4′,4′′-diaminotriphenylamine (DBDTA), was synthesized and characterized. A series of polyimides (PIs) were copolymerized from DBDTA, 3,3′-dimethyl-4,4′-methylenedianiline (DMMDA) and 4,4′-oxydiphthalic anhydride (ODPA) via a one-step method. The chemical structures of the diamine and PIs were characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (¹H NMR). Properties such as the solubility, rubbing resistance, thermal stability and pre-tilt angle of the PIs were investigated. Furthermore, the results were compared with the PIs-BZA derived from 4-dodecyloxy-biphenyl-3′,5′-diaminobenzoate (DBPDA). The PIs-TPA derived from DBDTA exhibited better transparency and thermal stability than the PIs-BZA from DBPDA. When the content of functional diamines was only 10%, the PI₁-TPA derived from DBDTA displayed better solubility than the PI₁-BZA from DBPDA. In addition, all PIs could induce uniform vertical alignment of the liquid crystals (LCs) before and after the rubbing process, but PI₁-BZA only induced parallel alignment of the LCs after rubbing process. It is suggested that the PI₁-TPA film is more resistant to the rubbing process than PI₁-BZA.