Well-distributed lithium amidoborane (LiAB) nanoparticles were successfully fabricated via adopting carbon nanofibers (CNFs) with homogenous pores uniformly containing Li3N as the nanoreactor and reactant, simply prepared by a single-nozzle electrospinning technique, for the subsequent interaction with AB. The hierarchical porous structure consists of various macropores, mesopores and micropores in situ produced during the formation of Li3N simultaneously serving as the reaction initiator, which not only controllably realizes the well-distribution of LiAB nanoparticles but also provides favorable channels for hydrogen release. Because of the hierarchical porous architecture and nanoscale size effects, the LiAB nanoparticles start to release hydrogen at only 40 °C, which is 30 °C lower than that of pure LiAB, and dehydrogenate completely within only 15 min at 100 °C (10.6 wt%). This work provides a new perspective to the controllable fabrication of nanosized hydrogen storage materials.