The use of Li3BN2H8 complex hydride as a practical hydrogen storage material is limited by its high desorption temperature and poor reversibility. While certain catalysts have been shown to decrease the dehydrogenation temperature, no significant improvement in reversibility has been reported thus far. In this study, we demonstrated that tuning the particle size to the nanometer scale by infiltration into nanoporous carbon scaffolds leads to dramatic improvements in the reversibility of Li3BN2H8. Possible changes in the dehydrogenation path were also observed in the nanoscaffolded hydride.