Supersaturated (Ti 0.5−x W 0.5 Cr x )B 2 (x = 0, 0.1, 0,2) solid solutions were produced by reaction sintering of transition metal diboride powders at a pressure of 60MPa at 1800°C. The formation kinetics of W 2 B 5 precipitates were investigated at lower temperatures by X-ray diffractometry (XRD) and secondary electron microscopy (SEM). The precipitation rate constants as a function of reciprocal temperature show non-monotonic behaviour in the range between 1450 and 1700°C with a maximum at about 1650°C. At low temperatures, Arrhenius behaviour is approximately valid, where the precipitation kinetics are dominated by the diffusion of the transition metals. In contrast, at temperatures higher than 1650°C, the precipitation rates decrease rapidly, since supersaturation, and consequently nucleation, is strongly reduced. The rate constants of precipitation are identical within error limits for Cr concentrations of x=0.1 and x = 0.2, however, they are significantly lower for x=0. This means that the addition of small amounts of Cr accelerates the precipitate formation, while further addition has no further influence. Samples resulting from powders which were high-energy milled with WC/Co hard balls before reaction sintering show an increased density of precipitated crystallites but no increased rate constants of precipitation. This result can be explained under the assumption that for these samples a significant amount of additional pre-existing nuclei was present before precipitation starts, which were formed by heterogeneous nucleation at Co impurities, introduced by the milling process.