In this study, we report on the fabrication and utilization of NiCr alloy nanoparticles (NPs)-decorated carbon nanofibers (CNFs) as efficient and competent non-precious catalysts for the hydrolytic dehydrogenation of ammonia borane (AB) at 25 ± 2 °C. The introduced NFs have been fabricated in one step using a high-temperature thermal decomposition of the prepared electrospun nanofiber mats (nickel acetate tetrahydrate, chromium acetate dimer, and polyvinyl alcohol) in an inert atmosphere. The chemical composition of the NFs with different proportions of NiCr (x = 0.0, 0.1, 0.15, 0.2, 0.25, 0.3) was established via standard characterization techniques. These techniques proved the formation of disorder CrNi alloy and carbon for all the formulations. The as-synthesized composite NFs exhibited a higher catalytic performance for AB dehydrogenation than that of Cr-free Ni-CNFs. Among all the formulations, the sample composed of 15% Cr shows the best catalytic performance, as more H was released in less time. Furthermore, it shows good stability, as it is recyclable with little decline in the catalytic activity after six cycles. It also demonstrates the activation energy, entropy (ΔS), and enthalpy (ΔH) with 37.6 kJ/mole, 0.094 kJ/mole, and 35.03 kJ/mole, respectively. Accordingly, the introduced catalyst has a lower price with higher performance encouraging a practical sustainable H energy application from the chemical hydrogen storage materials.