The hexagonal boron nitrides (BNs) with different morphologies are synthesized on a large scale by a simple route using a two-step synthetic process. The morphology of h-BN can be easily controlled by changing the heat-treatment atmosphere. The whiskers with 0.5–10 μm in diameter and 50–100 μm in length consist of few-layers nanosheets in the NH3 gas. The BN nanosheets can be dissociated from the whiskers by ultrasonic treatment, which are less than 5 nm in thickness and even only two layers thick. The concentration and activity of N play an important role, and abundant N and higher activity are conducive for refining grain in reaction. The H3BO3 and C3N6H6 molecules form a layer-like morphology with the interlinked planar triangle by a hydrogen-bonded structure.