ABSTRACTA new type of low‐molecular‐weight polypyrimidine in a π‐conjugated main chain was prepared by a Grignard reaction between 2‐amino‐4,6‐dichloropyrimidine and 1,4‐dibromo‐2,5‐didodecyloxybenzene in the presence of [1,2‐Bis(diphenylphosphino) ethane]dichloronickel(II). The structure of the copolymer was fully elucidated by Fourier transform infrared spectroscopy, 1H‐NMR, and elemental analysis. The copolymer had good solubility in common organic solvents. The copolymer displayed a bathochromic shift when protonated with an organic or inorganic acid in chloroform or tetrahydrofuran. The copolymer depicted facile p‐doping and good electron‐transporting electrochemical properties in a 1M H2SO4 aqueous solution. The copolymer showed a narrow polydispersity of 1.04. Thermogravimetric analysis showed that the copolymer had a certain thermal stability with no decomposition at a temperature of 250°C under N2. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41174.