China’s pollutant discharge permit system mandates total-quantity emission control for industrial volatile organic compounds (VOCs), yet the actual utilization of permitted capacity remains poorly studied. This study developed an “emission idle rate” (IR = 1 − actual/permitted emissions) framework and applied it to 130 chemical enterprises across three cities in Jiangsu Province using 2020–2024 panel data. The mean idle rate reached 78.1%, with no significant inter-city differences (H = 0.96, p = 0.619), attributable to both production underutilization and systematic over-estimation of emission ceilings inherent in the design-capacity-based permit methodology. Ward hierarchical clustering revealed three emission behavioral patterns: Persistent Surplus (n = 74, IR = 0.95), Declining Surplus (n = 32, IR = 0.69), and Growing Surplus (n = 19, IR = 0.59), exhibiting distinct idle rate levels and temporal trajectories. Cluster differentiation was significantly associated only with production-side emission characteristics, while enterprise economic variables showed no significant effects. The estimated tradeable emission surplus reached 668.3 t/a, though its realization faces transaction cost barriers including the lack of standardized transfer mechanisms and formal VOC trading infrastructure. A quadrant-based strategy matrix integrating idle rate levels with temporal trends is proposed for differentiated permit management.