AbstractHexagonal boron nitride (h‐BN) has received considerable attention, due to its high thermal conductivity and electrical insulation. However, the intrinsic platelike structure with the strong anisotropic property restricts its applications, and it is necessary to synthesize isotropic spherical h‐BN particles (SP‐BNs) with submicron size. Till now, methods to prepare (SP‐BN) still exist problems, such as high oxygen impurities and pollution, generated by the ammonia and pyrolysis of precursors. Here, a relatively green reaction between the restricted template of carbon nanospheres and boron trioxide (B₂O₃) under elevated temperature is conducted, and the SP‐BNs with an average diameter of 200–300 nm (named Nano‐BN‐s) have been successfully synthesized. Comprehensive scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction characterizations confirm the obtained products are spherical boron nitride. With the analysis of X‐ray photoelectron spectroscopy and Fourier transform infrared, the reaction mechanism is briefly discussed. These results indicate the reaction occurs on the restricted template of carbon nanospheres, and the C atoms are substituted by B and N atoms as the reaction progress, forming the Nano‐BN‐s. What is more, the restricted template method plays a key role in the design and improves h‐BN‐based materials in the future and may also be extended to form other novel materials.