SBA-15 (mesoporous SiO2) is used to stabilize and transfer F?in the NH4BF4 CVD reaction for the first time, and a large-scale crystalline h-BN phase can be prepared. We successfully fabricate hollow h-BN capsules with collapsed surfaces in our designed NH4BF4 CVD system. Optimum temperature conditions are obtained, and a detailed formation mechanism is further proposed. The successful SBA-15-assisted NH4BF4 CVD route is of importance and enriches the engineering technology in the h-BN single-source CVD reaction.