Substituted polythiophenes and polycarbazoles are materials of great interest as charge-carrier transport materials and have been utilized in PLED and FET applications. The layer-by-layer (LbL) self assembly has been used to fabricate polymer thin films on any substrates. The multilayer polymer thin films are constructed by alternating adsorption of anionic and cationic polymers. Polyelectrolyte multilayer ultrathin films containing anionic poly[2-(thiophen-3-yl)ethyl methacrylate-co-methacrylic acid] ; P(TEM-co-MA) and cationic poly[4-(9H-carbazol-9-yl)-N-buthyl-4-vinyl pyridium bromide]; P4VPCBZ, were fabricated. The growth of multilayer ultrathin films was followed by UV-vis absorption spectrophotometer and surface plasmon scpectroscopy (SPR). The deposition of P(TEM-co-MA) /P4VPCBZ as multilayer self-assembled ultrathin films regularly grow which showed linear growth of absorbance and thickness with increasing the number of layer pair. Cross-linking of the layers was verified by cyclic voltammetry (CV) with good electro-copolymerizability. ©2010 IEEE.