With recent findings of substantial amounts of B in rock-forming minerals, it has become evident a need exists for microprobe techniques allowing quantitative B determinations in minerals. A microprobe method based on the nuclear reaction 11B(p,α)2α has the potential to become a powerful tool for analyses of minerals with B contents spanning a wide concentration range. In this paper, we present nuclear microprobe analyses of B in a set of silicate minerals containing stoichiometric concentrations of B in the range 1.9–8.8 wt%. Our results strongly indicate that nuclear reaction analyses of silicates utilizing the 11B(p,α)2α nuclear reaction are virtually matrix-insensitive, and saturation effects are negligible within the studied range of B concentrations. This finding suggests that it is adequate to use a single B standard for calibration purposes for analyses covering wide ranges of B concentrations in silicates. In addition, we demonstrate how B-concentration maps of high contrast and resolution may be produced by scanning the proton beam over the samples.