Poly(arylene ether ketone)s are arguably the most important class of high-performance polymers. These polymers have excellent heat and chemical resistance which has been instrumental in their use in advanced composites. A vexing shortcoming of these polymers is their limited processability. We now report a novel nucleophilic carbon-carbon bond-forming polymerization route for the synthesis of new poly(arylene ketone sulfone)s, devoid of any ether linkages in the backbone, via soluble precursors. These polymers can be synthesized at moderate temperatures and in high yields.