Understanding of the structural complexities of metal-metalloid nanoparticles is at the heart of several proposals for investigating the physical properties and practical applications of these bi-elemental nanomaterials. To date, the most widely studied metal-metalloid is the nickel-boron (Ni.B) system; however, the exact nature of the structure of the material itself has remained unclear. Herein we show our systematic investigations of the material in an attempt to reveal its fascinating nanostructure. The relation between its high catalytic activity and the ultrafine structure is explored, and the work has been further extended to the formation of colloidal Ni.B nanoparticles. The results presented in this work may represent a substantial progress toward a full understanding of the nickel-boron chemistry.