The electropolymerization behaviors of an electroactive and luminescent compound TCPC as precursor are studied. The resultant electrochemical deposition (ED) films are characterized by cyclic voltammetry (CV), UV-vis, fluorescence spectra, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Under the CV mode with potential range of -0.5 to 0.85 V vs Ag/Ag(+), the coupling reactions between the carbazole units of TCPC are very efficient, while the fluorescent trifluorene segment in TCPC is chemically inert in this potential range, which results in a highly fluorescent film formation on indium tin oxide (ITO) electrode. The deposition parameters for preparing the TCPC-based ED films are optimized, and the best ED film gives the fluorescence efficiency of 45.5% with surface roughness of 2.8 nm and morphologic stability as heating to 180 degrees C. The light-emitting devices (LEDs) using this ED film as light emitting layer with structure ITO/ED film (approximately 100 nm)/Ba/Al achieve maximum luminescence and external quantum efficiency of 4224 cd/m(2) at 17 V and 0.72% at 11.5 V, respectively, which are better than the device using TCPC spin-coating films as emitting layer. The technique provides a facile route toward a patternable luminescent film and device because such luminescent ED films can be manipulatively deposited on the electrified electrode.