Mild steel offers versatile properties at lower costs. This has given the alloy a large application base in the industry. However, the increasing complexity and severity of service environments have shifted the focus of many industries to structure modification techniques, like physical vapor deposition to improve material properties and performance. Synthesis of WC-Co thin films by physical vapor deposition technology has attracted great research interest owing to the outstanding mechanical properties of the material and its potential to be utilized extreme engineering applications such as in wear-resistance, heavy cutting and excavation industries. The growth in the use of WC-Co thin films in the general mechanical industry is however slow due to lack of data on the tribological characteristics of WC-Co coated materials. Control and manipulation of synthesis parameters are of significant concern in order to tailor such material properties and performance. The focus of this paper is to, therefore, investigate the effect of Rf magnetron power and deposition temperature on the structure and sliding wear behavior of WC-Co thin film. The surface morphology and nature were acquired using x-ray photoelectron spectroscopy (XPS) and Grazing Incidence x-ray absorption spectroscopy (GI-XAS). To validate the synchrotron results, additional analysis was acquired from Scanning electron microscopy (SEM), Raman spectroscopy and surface profilometry to predict and point out optimum synthesis parameters for best properties of the film. Finally, the wear performance of the film-substrate system was determined and reported.