A new type - pi-conjugated copolymers of 2-amino-pyrimidine was prepared between 2-amino-4,6-diiodidepyrimidine and 1,4-dibromo-2,5-dialkoxybenzene by Sonogashira polycondensation. The structures of the copolymers were elucidated by FT-IR, H-1 NMR and C-13 NMR, fluorescence spectroscopy, gel permeation chromatography, thermal analysis and element analysis. The derived polymers were soluble in common organic solvents and trifloroacetic acid and exhibited good thermal stability. They emitted green light under UV irradiation in solid state and blue or green light in solution phase, respectively. Electrochemical behavior of these new polymers depicted facile p-doping and good electron-transporting properties. These polymers displayed bathochromic shift when protonated with CH3SO3H acid in chloroform solutions or m-cresol solutions and the red-shifted peaks were observed from 490 nm to 652 nm. XRD patterns of copolymers showed that the intensity of peaks was enhanced with increasing alkyloxy chain length. (C) 2009 Elsevier Ltd. All rights reserved.