In this paper, we report the synthesis, characterization and optical properties of a donor-acceptor conjugated polymer, PTh-CN, containing 3,4-didodecyloxythiophene and cyanovinylene units. The polymer possesses a low band gap of 1.75 eV as calculated from the onset absorption edge. From the electrochemical study, the HOMO and LUMO energy levels of the polymer are figured out to be −5.52 eV and −3.52 eV, respectively. Polymer light-emitting diodes are fabricated using PTh-CN as the emissive layer with a device configuration of ITO/PEDOT:PSS/PTh-CN/Al. The device showed stable saturated red electroluminescence with CIE coordinate values (0.65, 0.32) at 12 V, which are very close to the values for standard red demanded by the NTSC. In addition, the device showed good colour stability under different bias voltages and the threshold voltage of the PLED device is found to be as low as 3.1 V. Further, a nanocomposite of the polymer and TiO2 nanoparticles is prepared by the dispersion method. The nonlinear optical properties of PTh-CN and PTh-CN/TiO2 nanocomposite are studied using z-scan technique. The polymer solution, polymer film and polymer/TiO2 nanocomposite film show a strong saturable absorption behaviour. The value of saturation intensity (Is) is found to be of the order 1011-1012 W/m2, indicating that the materials are useful candidates for photonic applications.