This study developed a Cr-modified CuFe/HZSM-5 catalyst coupled with a dielectric barrier discharge (DBD) plasma reactor, achieving highly efficient conversion of CO₂ and CH₄ into higher-value alcohols under ambient temperature and pressure. Characterization and catalytic performance evaluations demonstrated that appropriate Cr doping enhances CuFe metal dispersion, strengthens Cu-Fe electronic interactions, and improves CO? adsorption and activation capabilities. Compared to CuFe/ZSM-5, the introduction of Cr increased alcohol selectivity by 5.3%. Under the synergistic effect of plasma-catalysis, the system achieved CO₂ and CH₄ conversion rates of 23.9% and 24.1%, respectively, with liquid product selectivity reaching 50.5%, of which alcohols accounted for 83% (including methanol, ethanol, and C₃ alcohols). The gaseous products were primarily CO (24.1%) and light hydrocarbons. Reaction pathway studies revealed that plasma activation generates .CH_x and .CO radicals, which undergo C-C coupling and hydrogenation at the Cr-modified Cu-Fe interface, selectively forming C₂₊ oxygenated products. This work provides an efficient catalytic strategy for the resource utilization of greenhouse gases.