As electrode material for pseudocapacitors, polyaniline (PANI) can be subject to irreversible oxidation and volume changes during the ion insertion-deinsertion process in the charge-discharge procedure that reduces cycle life and electrode capacity, thus, limiting its widespread application. Here, triphenylamine (TPA) was copolymerized with aniline via the facile chemical oxidative polymerization. TEM analysis showed that the products were well-defined nanotubes, and their lengths and diameters increased with increasing the feeding ratio of TPA. By introducing TPA units, the copolymer P(ANI-TPA) nanotubes exhibited photofluorescence and the fluorescence emission intensity at 430nm decreased with decreasing the media pH values. Their specific capacitance and electrochemical cyclic stability were enhanced when being used as the electrode materials for supercapacitors, compared with the homopolymer PANI. The copolymer P(ANI-TPA) nanotubes with unique morphology developed in the present work strengthen the applications of conductive polymer nanomaterials as supercapacitors, photoluminescence devices and pH sensors.