In this paper we describe the large-scale synthesis of inorganic fullerene-like (IF-like) hexagonal boron nitride with vessel, hollow sphere, peanut, and onion structures by reacting BBr3 with the synergic nitrogen sources NaNH2 and NH4Cl at 400-450 degreesC for 6-12 h. The composition of products could be confirmed to be pure boron nitride with hexagonal structures by the XRD patterns and FT-IF, XPS, and EDXA spectra. The representative HRTEM images clearly reveal the layerlike features of the products. Here, the peanut-like structure of the IF-like BN is reported for the first time, and added to the list as one kind of new morphology of BN nanomaterials. The similarity in the structure between h-BN and graphite is responsible for the formation of IF-like BN with nanostructures of vessels, hollow spheres, peanuts, and onions.