The opportunity for efficient hydrogen extraction from natural gas through perovskite-supported Ni5 nanocluster has been investigated using first-principles calculations. The reaction dynamics of dry reforming of methane (DRM) has been studied, and all the elementary steps are assessed to locate the transition states. The obtained results demonstrate a high affinity of CH4 and CO2 towards the supported nanocluster as predicted by reasonably large adsorption energies. Chromium and Molybdenum on the perovskite surface play an essential role, in conjunction with Nickel, in methane CH bond activation. Ni2Cr and Ni2Mo are identified as the sites where methane reaction begins and ends, or vice versa. The dissociation of CO2 is also facilitated by the nanocluster, with the rate-limiting step in the two pathways being CH4 dissociation. The study suggests that decorating the anode with Ni-nanoclusters can effectively promote hydrogen extraction from hydrocarbon fuels in solid-oxide fuel cells.