Co-0 nanoparticles supported on TiO2 nanofibers (nanocomposite) were prepared using a simple electrospinning technique and in-situ chemical reduction. The synthesized nanocomposite was used to generate hydrogen from ammonia borane (AB). Standard characterization techniques revealed dense distribution of Co-0 nanoparticles (Co NPs) onto the TiO2 nanofibers (TiO2 NFs) in the prepared nanocomposite. The introduced nanocomposite has been showed a good catalytic activity as compared to those unsupported Co NPs. As, the hydrogen evolutions for the nanocomposite and Co NPs were 3 mol in 23 min and 47 min, respectively. Furthermore, both the nanocomposite concentration and the temperature have a significant catalytic activity in the AB dehydrogenation. The nanocomposite also showed low effective activation energy of similar to 26.03 KJ center dot mol(-1).