Bisfunctional biphenylene monomers were designed, synthesized, and inspected as building blocks for aromatic polyketone synthesis. Starting from 2,2＇-dimethoxybiphenylene (1), a highly activated acyl-acceptant biphenylene monomer affording high molecular weight polyketones, two types of biphenylene monomers were developed: 5,5＇-bis(3[4]-chlorobenzoyl)-2,2＇-dimethoxybiphenylenes (6) which readily gave the corresponding polyketones by nickel-catalyzed aromatic coupling polymerization and 2,2＇-bis(trifluoromethyl)-4,4＇-biphenylenedicarboxylic acid (27) which reacted with biphenylene 1 in P2O5-CH3SO3H to give the corresponding fluorinated aromatic polyketone, selectively. The related model reactions for both monomer synthesis and polymerization were also investigated.