The article deals with the pretreatment technique for preparing the surface of aluminum alloy EN AW 5754 before thermal spray. The surface after different pretreatments, including degreasing with acetone, chemical etching with acidic and alkali solutions, grit-blasting, cathodic cleaning, and some combinations of these techniques, has been studied. The investigation of pre-treated surfaces covered the topographical study (using scanning electron microscopy, atomic force microscopy, and 3D profilometry), the chemical analysis by x-ray photoelectron spectroscopy, the evaluation of surface wettability (sessile drop method), and the assessment of surface free energy. Compared with all the techniques used in present work, the cathodic cleaning and its combination with grit-blasting provide the most preferable chemistry of the surface. Due to the absence of hydroxides at the surface and, possible, due to the diffusion of magnesium to the surface of substrate, the surface wettability and the surface free energy have been significantly improved. No direct correlation between the surface topography and the surface wettability has been established.