We present here the first studies on copolymer layers obtained from electrosynthesis of pyrrole and salen compounds. This work comes into the field of modified electrodes for sensoring applications. We. investigated this electro-copolymerization because the coupling occurs by radical cation (RC) coupling for both compounds. The electrochemical behavior was studied by cyclic voltammetry, spectroelectrochemistry and in situ electron spin resonance (ESR); quantitative characterization was performed with electron dispersive spectroscopy and mass spectrometry (Maldi-Tof). In the case of the copolymer prepared with little pyrrole (versus salen) in the starting solution, the ESR data gave no typical PPy signal although cyclic voltammograms (CVs) were completely different from those of poly(salen). The composition of the layers is estimated with good approximation and this is evidently an interesting material for sensoring applications such as gas (vapor) or heavy metal sensors.