The optimization of processing plants is one of the main concerns in the mining industry, since the comminution stage, a fundamental operation, accounts for up to 70% of total energy consumption. The aim of this study was to determine the effects that ball size and mill speed exert on the milling kinetics over a wide range of particle sizes. This was done through dry milling and batch grinding tests performed on two samples from the Penouta Sn–Ta–Nb mine (Galicia, Spain), and following Austin methodology. In addition, the relationships amongst Sn, Ta and Nb content, as metals of interest, the specific rate of breakage Si, the kinetic parameters, and the operational conditions were studied through X-Ray fluorescence (XRF) techniques. The results show that, overall, the specific rate of breakage Si decreases with decreasing feed particle size and increasing ball size for most of the tested conditions. A selection function, αT, was formulated on the basis of the ball size for both Penouta mine samples. Finally, it was found that there does exist a direct relationship amongst Sn, Ta and Nb content, as metals of interest, in the milling product, the specific rate of breakage Si and the operational–mineralogical variables of ball size, mill speed and feed particle size.