Novel polyaryleneethynylenes having a diphenylmaleimide group in the main chain, PDPMIPPE and PDPMIMPE, were prepared by a Pd(0)/Cu(I)-catalyzed coupling reaction in nearly quantitative yields. The polymers v,,ere soluble in common organic solvents such as chloroform, toluene, and tetrahydrofuran and gave robust and glassy films by a spin-coating technique. The polymer showed thermal curing process in the range of 165-250 degreesC by crosslinking between acetylenic groups. The polymer solutions in tetrahydrofuran showed yellowish green-colored photoluminescence. (C) 2002 Elsevier Science B.V. All rights reserved.