The electrification of diverse chemical processes with renewable electricity is considered to be an attractive solution to the issue of global warming, which is becoming continuously more severe. Plasma can be an effective supplier of heat during electrification. Here, we achieve a highly selective conversion of toluene (C7H8) to acetylene (C2H2) using rotating-arc plasma, which is a capable means of upcycling industrial waste into value-added materials. Compared to other processes involving treatment or oxidation to eliminate low concentrations of C7H8, the proposed approach shows the conversion of high concentrations of C7H8 to C2H2. Based on parametric studies on the effect of the residence time, specific energy input, reactant concentration, and simulation, the highest reported C2H2 selectivity and energy efficiency are obtained. The results suggest that plasma can act as an effective source of thermal activation and rotating-arc plasma can be a promising means to achieving electrification in the chemical industry.