Boron is a biologically important element, but its distribution in the natural environment and its behavior during many geological processes is not fully understood. In most metamorphic and igneous environments, boron is incorporated into minerals of the tourmaline supergroup. In high-grade metamorphic terranes like that of the Adirondack region of northern New York State, uncommon rock compositions combined with unusual and variable geologic conditions resulted in the formation of many additional boron-bearing minerals. This paper reviews the occurrences and geological settings of twelve relatively uncommon boron-bearing minerals in the southern Grenville Province of upstate New York and provides new chemical and Raman spectral data for seven of these minerals. The boron minerals range from relatively simple metal borates (e.g., vonsenite), to chemically complex borosilicates (e.g., prismatine), to a relatively rare borosilicate-carbonate (e.g., harkerite). Some are of primary igneous origin, while others are formed by a variety of prograde and retrograde metamorphic processes or by metasomatic/hydrothermal processes. Most of the boron minerals are formed within, or adjacent to, metasedimentary lithologies that surround the anorthositic massifs of the central Adirondacks. The metasedimentary rocks are thought to be the source of most of the boron, although additional boron isotope studies are needed to confirm this and to constrain the mechanisms of the formation of these unusual minerals.