Electroless copper metallization of polyphenylquinoxaline (PPQ) was carried out using a palladium acetyl acetonate (Pd(acac)2) precursor. A continuous wave Ar ion laser was used to decompose the Pd(acac)2 organometallic layer deposited onto the PPQ. The samples were then processed in a copper electroless plating solution of conventional composition. The sample surfaces were analysed by X-ray photoelectron spectroscopy before any treatment, after laser irradiation and at the very first stages of copper growth. An estimate of the temperature reached by the polymer under the laser beam was obtained by analysing the interference pattern reflected by the surface. Breakdown fields of the polymer dielectric were found in the region of 1 MV cm-1 and are weakly affected by the electrochemical processes.