A non-aqueous route and process for preparation of boron nitride utilizing aerosol assisted vapor phase synthesis (AAVS) wherein boron precursors are nitrided in one or two heating steps, and wherein a boron oxide nitride carbide intermediary composition is formed after the first heating step and may be further nitrided to form resultant spheroidal boron nitride powders including dense or hollow spheroidal particles that are smooth, bladed, dense or hollow, have protruding whiskers, and are of turbostratic or hexagonal crystalline structure, specifically wherein the boron precursor is dissolved in a non-aqueous solution prior to aerosolization.