The aim of this study was to examine the influence of particle size and extent of coating on the diffuse-reflectance spectra of wax matrices containing embedded potassium chloride. Near-infrared spectroscopy was used to analyse the diffuse-reflectance characteristics of the prepared multi-particulate matrices without destructive sample preparation. A 2-factor, 3-level face-centred central composite design was selected to construct a second-order polynomial model which described the effect of particle size and amount of coating on the intensity of the diffusely reflected light. A non-linear model was used to demonstrate the effect of the selected parameters on the intensity of the reflected light; good correlation was obtained between experimental and predicted results. The results indicated that the extent of coating and the particle size of the examined systems in the selected particle size-range modified the intensity of the reflected light. It can be concluded that near-infrared spectroscopy is a sensitive means of measuring not only the particle size of powders (substrates and their mixtures), but also that of coated multi-particulate systems.