The integration of non-thermal plasma (NTP) with heterogeneous catalysis has emerged as a promising strategy for the efficient abatement of industrial volatile organic compounds (VOCs), overcoming key limitations of conventional thermal and standalone plasma technologies. This review provides a comprehensive overview of the synergistic mechanisms in NTP-catalytic systems, with particular emphasis on the bidirectional interactions between plasma and the catalyst. Specifically, plasma can activate catalysts through surface defect generation and improved metal dispersion, while catalysts, in turn, modulate plasma characteristics via localized electric field enhancement and electron energy redistribution. Furthermore, this synergy spans multiple spatiotemporal scales, linking ultrafast electron dynamics with macroscopic catalytic performance, and atomic-scale active sites with reactor-level behavior. Based on these mechanistic insights, rational catalyst design strategies are systematically discussed, including transition metal oxides, noble metals, perovskites, and metal–organic frameworks. Finally, key challenges related to catalyst deactivation, energy efficiency, and process scalability are highlighted. Future perspectives are proposed, focusing on advanced in situ diagnostics and AI-assisted material discovery to accelerate the practical implementation of NTP-catalytic technologies for sustainable VOC removal.