Co-TiC nanoparticles (NPs)-like superficial protrusions were grown on the surface of electrospun carbon nanofibers to produce composite nanofibers (composite NFs). The composite NFs demonstrated good catalytic activity in hydrogen production through hydrolysis of an aqueous ammonia borane (AB) solution. Catalytic activities of composite NFs were compared with those of CoTiC/C NPs (composite NPs), Co/carbon nanofibers (Co/C NFs) and Co nanoparticles (Co NPs). The composite NFs showed the highest catalytic activity (0.4167molmin−1) compared to CoTiC/C NPs (0.35molmin−1), Co/C NFs (0.25molmin−1), and Co NPs (0.13molmin−1). The turn over frequency (TOF) value of the synthesized nanocomposite is determined to be 32.18molH2min−1(molmetal−1). Moreover, the composite NFs showed high stability, and could be reused for several cycles without makeup, reactivation, or regeneration. Kinetic studies showed that the rate of AB hydrolysis depends on the catalyst concentration and temperature; the activation energy was found to be ~ 26.19kJmol−1.