Poly[2-(tert-butoxycarbonyl)-1,4-phenyle] (2) was prepared by the Ni-catalyzed polymerization of tert-butyl 2,5-dichlorobenzoate (1). The microstructure of polymer 2 was probably alternating head-to-head and tail-to-tail. This polymer was soluble in dipolar aprotic solvents, chloroform, tetrahydrofuran, and dichloromethane. Polymer 2 was saponified easily by thermal or acid treatment to yield poly[2-carboxy-1,4-phenylene] (3). Decarboxylation of polymer 3 in quinoline in the presence of copper(II) oxide produced poly(p-phenylene) (PPP) (4).