A novel series of phthalazinone-based poly(arylene ether nitrile)s bearing terminal cyano groups via N-C linkages (PPEN-DCs) were synthesized by a simple solution polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HPPZ) with calculated 2,6-difluorobenzonitrile (DFBN), followed by the termination of 4-chlorobenzonitrile (CBN). The M(n)s of oligomeric PPEN-DCs, which are in the range of 1600-6200, can be well-controlled by adjusting reactant ratio. The incorporation of phthalazinone into the polymer chain results in an improvement in the solubility and glass transition temperatures (T(g)s). The amorphous PPEN-DCs were thermally crosslinked to afford insoluble products in the presence of terephthalonitrile and zinc chloride. The pendant cyano groups in the polymer chain hardly undergo any crosslinking or cyclization, while the terminal cyano, groups with nitrogen-bridged phthalazinone in the para-substitution are much more reactive in s-triazine forming reaction and effectively promote certain crosslinking under normal pressure. T(g)s of the oligomers, which range from 245 to 269 degrees C, could be further increased at least by 94 degrees C upon thermal curing. The crosslinked samples exhibit excellent thermal stability and absorb less than 2.7 wt% water after exposure to an aqueous environment for extended periods. This kind of cyano-terminated poly(arylene ether nitrile)s may be a good candidate as matrix resins for high-performance polymeric materials. (C) 2009 Elsevier Ltd. All rights reserved.