Conjugated-non-conjugated alternating block copolymers containing cyano-modified distirylbenzene units as emitting chromophores were synthesized via Knoevenagel and Wittig reactions; the non-conjugated block was an alkylene spacer. The polymers were differentiated with respect to the location of the cyano groups in the chromophoric block (double bond or phenylene ring). When photoluminescence and electroluminescence spectra of these materials were compared with those of a similar structure without the cyano group, a strong bathochromic effect was observed. A more pronounced red shift and a higher electroluminescence efficiency was observed in the polymer with the cyano group attached to the aromatic ring.