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There has recently been intense research on boron nitride (BN)-based materials for radiation shielding, including shielding neutron radiations from nuclear reactors. However, advanced materials should display more than just radiation-shielding functions to be considered to be an outstanding candidate for applications in space; consequently, multifunctional BN-based materials with high hydrogen intake have been found to provide sufficient shielding properties. This article reviews the BN nanostructures and BN-based materials for space radiation-shielding application. It begins with a brief introduction of BN structures and their physical properties and followed by an emphasis on radiation-shielding properties of BN as related to neutron capture and hydrogen storage. In addition, development of BN-based materials for a space radiation-shielding application is discussed.