Application of an anodic potential under recycled argon atmosphere to a highly concentrated solution of N‐vinyl‐2‐pyrrolidone (5 mol.dm−3) allows to graft and polymerise the monomer onto a Pt or Au electrode. XPS, UPS and IRRAS spectroscopies reveal the presence of thin PVP films on these surfaces. XPS data point to the formation of C‐metal bonds and support the grafting hypothesis of polymer chains onto the surface of the electrode. XPS and UPS studies performed after annealing indicate that the different structures of the polymer are stable up to 200 °C under ultra high vacuum and confirm the chemisorbed nature of the surface bond. A cationic mechanism is proposed for the grafting and the polymerisation. Preliminary attempts to relax the preparation conditions show that films can be obtained in ambient atmospheric conditions, but their thickness is reduced compared to those obtained under recycled argon conditions. ©1996 American Institute of Physics.