Two novel D-A polymers containing pyridine with vinylene spacer, P1 and P2 were synthesised through Heck polymerisation. In both the polymers, pyridine is linked with two donor phenylene at position-4 and -6, and electron withdrawing cyano group at position-3. Additionally, P1 possess methoxy side chain at position-2 of 3-cyanopyridine and P2 is flanked with both methoxy and octyloxy side chain at alternate pyridine. The polymers are well characterised with ¹H-NMR, UV–Vis absorption, PL, GPC, TGA, cyclic voltammetry and AFM. TGA data reveal that the polymers P1 and P2 are thermally stable up to 350–400 °C. The UV–Vis absorption spectra for solid thin films envisage efficient molecular stacking with red shifting the absorption maxima to 30 nm when compared to solution. The obtained polymers have a band gap of 1.8–1.93 eV with low laying HOMO and LUMO energy level. The polymers displayed very good blue fluorescence in CHCl₃ upon irradiated with UV light (254 nm) and Atomic force microscopy (AFM) applications to polymer P1 and P2 surfaces are providing interesting images of nanometre-scale polymer structures.