This paper describes peel adhesion of solvent-borne acrylic pressure-sensitive adhesives (PSA) crosslinked using crosslinking agent aluminum acetylacetonate (AlACA). The peel adhesion of acrylic PSA crosslinked with AlACA was evaluated as a function of adhesive coating weight and kind of tested substrates characterized by various surface free energies (SFE). The diverse substrates tested were stainless steel, poly(methyl methacrylate) (PMMA), polycarbonate (PC), polyethylene (PE), polypropylene (PP) and polytetrafluoroethylene (PTFE) known as Teflon. For peel adhesion determination the most common method in the adhesive tape and PSA industries was used. In order to evaluate surface free energies (SFE) of materials used in tack measurements the Owens–Wendt (OW) and van Oss–Chaudhury–Good (vOCG) methods were employed. The conducted experiments have shown, that a clear relationship exists between SFE of the substrate and peel adhesion of model acrylic PSA. In general, an increase of the difference in SFE between the substrate and adhesive (ΔSFE) affects positive peel adhesion.