The physical and mechanical properties of laminates can be influenced by the types, general characteristics, and pressing conditions of the papers and resins used in their production. The goal of this study was to determine the effect of layer structure on some of the physical and mechanical characteristics of high-pressure laminates (HPL). Laminates with five different layer structures were produced. Laminate types included standard laminate, laminate with a barrier layer, laminate with a barrier and an overlay, laminate with an overlay, and laminate with a barrier and an aluminum oxide overlay. Specimens chosen from these laminates were subjected to resistance to wear, scratching, staining, steam, dry heat, cigarette burns, cracking, breaking, and color change under xenon arc lamp light tests. Specimens were also subjected to immersion in boiling water tests in conformance with the EN 438 standards. Results obtained from these tests showed that the arrangement of different layers does not influence resistance to cracking, breaking, or change of color under xenon arc lamp light but does influence the other resistance characteristics. Use of an aluminum oxide overlay positively contributes to all of the resistance characteristics.