Milk powder is an important ingredient in the confectionery industry, but its variable nature has consequences for the quality of the final confectionary product. This paper demonstrates that skim milk powders (SMP) produced using different (but typical) manufacturing processes, when used as ingredients in the manufacture of model white chocolates, had a significant impact on the sensory and volatile profiles of the chocolate. SMP was produced from raw bovine milk using either low or high heat treatment, and a model white chocolate was prepared from each SMP. A directional discrimination test with naïve panelists showed that the chocolate prepared from the high heat SMP had more caramel/fudge character (p < 0.0001), and sensory profiling with an expert panel showed an increase in both fudge (p < 0.05) and condensed milk (p < 0.05) flavor. Gas chromatography (GC)-mass spectrometry and GC-olfactometry of both the SMPs and the model chocolates showed a concomitant increase in Maillard-derived volatiles which are likely to account for this change in flavor.