The Thermionic Vacuum Arc (TVA) is an original deposition method using a combination of anodic arc and powerful electron gun system (up to 600 W) for the growth of thin films from solid precursors under a vacuum of 10−4 Pa. The advantage of this technology is the comparatively high deposition rate while keeping good properties of the deposited films. The aim of this paper is to report on the characterization of the Mg and Mg–Zn thin films deposited by the TVA method. By careful selection of the deposition parameters, we have achieved a rather stable discharge that resulted in good film properties. The surface morphology and wettability of the deposited Mg and Mg–Zn thin films were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and free surface energy (FSE) by surface energy evaluation system. The results revealed that the size of crystallites is 5.0 nm in the case of Mg–Zn/Si and 6.5 nm in the case of Mg/Si sample; a promising result for future applications of the TVA. The film properties are complemented by plasma parameters measured by a heated probe.