p-Dibromo xylene, a typical atom transfer radical polymerization (ATRP) bifunctional initiator, was polymerized in atom transfer radical coupling (ATRC) conditions, yielding poly(p-xylylene). In order to confirm the success of the reaction by H-1-NMR spectroscopy and GPC, a more soluble product, poly(methyl methacrylate-b-p-phenylene-ethylene), was also synthesized by adding 5% poly(methyl methacrylate) with an activated bromine atom at the chain end obtained by ATRP to the polymerization feed. The H-1-NMR spectrum shows the presence of poly(p-xylylene) component in the co-polymer. The GPC measurement also shows an increase of molecular weight together with a decrease of polydispersity, proving the formation of the co-polymer. The method described here opens a new pathway for synthesis of polymers from various classes by using appropriate ATRP bifunctional initiators as monomer, in ATRC or even ATRP conditions.