We report here a synthetic route to unsymmetric cyanosubstituted oligo(p-phenylene-vinylene)s (COPVs), which have not been reported so far. These molecules were synthesised in high yield through a simple pathway of step-wise Knoevenagel condensation. The proposed study improves the molecular design strategies of COPVs towards solid fluorescent materials. This synthetic pathway gives various novel COPVs. The properties of the obtained COPVs are also discussed.