Natural gas is one of the foremost basic energy sources on earth. Although biological process appears as promising valorization routes to transfer biomass to sustainable methane, the recalcitrance of lignocellulosic biomass is the major limitation for the production of mixing gas to meet the natural gas composition of pipeline transportation. Here we develop a catalytic-drive approach to directly transfer solid biomass to bio-natural gas which can be suitable for the current infrastructure. A catalyst with Ni₂Al₃ alloy phase enables nearly complete conversion of various agricultural and forestry residues, the total carbon yield of gas products reaches up to 93% after several hours at relative low-temperature (300 degrees Celsius). And the catalyst shows powerful processing capability for the production of natural gas during thirty cycles. A low-carbon footprint is estimated by a preliminary life cycle assessment, especially for the low hydrogen pressure and non-fossil hydrogen, and technical economic analysis predicts that this process is an economically competitive production process.