A set of novel Y-shaped asymmetrical pyrimidines has been prepared on the basis of 2-hydroxy-4,6-dimethylpyrimidine used as a starting compound. All of them are the chromophores of D-π-A-π-D' motif where A is a central pyrimidine core; D, D' are the thiophene-2-yl, thiophene-3-yl, 9-ethyl-9H-carbazol-3-yl or 9H-carbazole-9-yl-fragments and a π-bridge is a vinyl or styryl moiety. We have studied their optical, electrochemical and electrophysical characteristics, as well as their polymerizability with the help of electrochemical oxidation.