Tris-(p-aminophenoxy)phosphineoxide, t-APPO, was prepared from 4-nitrophenol and POCl3, followed by hydrogenation. A series of polyimides prepared from t-APPO and the corresponding dianhydrides by two-stage polycondensation method was characterized by Fourier Transform Infrared Spectrometer (FTIR), GPC, thermal analysis and physical methods. Moreover, in order to check the permeation properties of the resulting polyimide film, the selectivity of the polyimide-coated electrode toward electroactive species (ascorbic acid and dopamine) was examined by means of cyclic voltammetry (CV), differential pulse voltammetry (DPV) and time-base amperometric measurement (TB) techniques. As a result, it has been found that polyimide electrode showed selective permeation for dopamine while blocking the permeation of ascorbic acid through film. Therefore, it has been claimed that phosphine oxide-containing polyimide electrode can be used as a dopamine-selective membrane in the presence of ascorbic acid.