<p>Coal-fired power generation is one of the main methods of electricity production around the world. However, this process suffers from large amounts of GHG emissions. Combining CO₂ captured from its flue gas with green hydrogen for producing methanol is considered a promising energy pathway. To address the problem of high energy consumption in the CO₂ capture, this study proposes novel coal/biomass chemical looping combustion coupling with green hydrogen for co-production of electricity and methanol processes. Results show that the net electricity efficiencies of coal, biomass, and coal-biomass chemical looping combustion power plants are 4.35, 2.63, and 3.75 percentage point higher than that of coal-fired power plant, whose efficiency is only 37.89%. In addition, the energy efficiencies of the coupling systems for co-producing electricity and methanol systems are improved from 53.02% of the basic process to 63.25%, 62.59%, and 63.02%. The net power generation and methanol output of the coupling system with coal chemical looping combustion are the highest with 688.53&#xa0;MW and 386.34 t/h, while those of the coupling system with biomass chemical looping combustion are the lowest with 351.53&#xa0;MW and 207.8 t/h. For the economic aspect, the methanol product costs of the coupling systems with coal, biomass, and coal-biomass chemical looping combustion are nearly 5185 RMB/t, which are 274 RMB/t lower than that of the coupling system with coal conventional combustion. The above data provide techno-economic reference for solving the high carbon emission problem of power plants and producing methanol.</p>