<h2>Summary</h2> Synergy between plasma and catalysis has long been recognized, but efforts to improve synergy and energy efficiency remain both highly desirable and challenging. Herein, β-Mo<sub>2</sub>C nanorods were coupled with non-thermal plasma (NTP) to catalyze selective CO<sub>2</sub> reduction to CO by H<sub>2</sub> or CH<sub>4</sub>. Unprecedented catalytic activity and selectivity were achieved without additional thermal input, and the turnover frequency (TOF) was an order of magnitude higher than that obtained during thermal catalysis. The porous-structured β-Mo<sub>2</sub>C nanorods not only possessed large accessible surfaces but also facilitated charge deposition to generate a strong local electric field when NTP was coupled. The interplay between β-Mo<sub>2</sub>C nanorods and NTP boosted the synergy and energy efficiency: the TOF and CO specific energy yield were 1.4–2 times and ∼10 times higher, respectively, than those of β-Mo<sub>2</sub>C nanoparticles. This strategy of coupling regularly shaped catalytic materials with NTP provides new opportunities to improve the efficiency of plasma-assisted catalytic processes.