A promising method for the production of few-layer graphene (FLG) is microwave plasma-enhanced chemical vapour deposition (MW PECVD). However, the growth mechanism of PECVD-synthesized FLG is not completely understood. The aim of this work was to investigate the initial stages of the growth process of FLG deposited by MW PECVD on several substrates (quartz, silicon, platinum). The deposited thin films were characterized by angle-resolved x-ray photoelectron spectroscopy (ARXPS), electron backscattered diffraction (EBSD), scanning electron microscopy (SEM) and x-ray diffraction (XRD). It was found that the initial stages of the deposition were different for the three chosen substrate materials. However, the fully grown FLG layers were similar for all substrates.