Large electric gradients are required for a variety of new applications, notably including the extreme high brightness electron sources for X-ray free electron lasers (FELs), radio-frequency (RF) photo-injectors, industrial and medical accelerators, and linear accelerators for particle physics colliders. In the framework of the INFN-LNF, SLAC (USA), KEK (Japan), UCLA (Los Angeles) collaboration, the Frascati National Laboratories (LNF) are involved in the modelling, development, and testing of RF structures devoted to particles acceleration by high gradient electric fields of particles through metal devices. In order to improve the maximum sustainable gradients in normal-conducting RF-accelerating structures, both the RF breakdown and dark current should be minimized. To this purpose, studying new materials as well as manufacturing techniques are mandatory to identify better solutions to such extremely requested applications. In this contribution, we discuss the possibility of using a dedicated coating on a solid copper sample (and other metals) with a relatively thick film to improve and optimize breakdown performances and to minimize the dark current. We present here the first characterization of MoO3 films deposited on copper by pulsed-laser deposition (PLD).