<p>Fresh-cut vegetables commonly incur postharvest mechanical injury and early microbial invasion markedly upregulating pectinase expression. Pectinase could catalyze the degradation of cell wall pectin, accelerate tissue softening, and increase spoilage. This study innovatively developed a pectin-gated system for food quality preservation. The system comprises a coaxially electrospun nanofiber pad in which carbon dots (Cu–pCDs) are embedded as emulsion stabilizers, with carvacrol (CAR) encapsulated in the core. To enhance mechanical strength and moisture retention, a polycaprolactone coating was subsequently applied onto the pad surface. Under normal storage conditions, the pad exhibited a moderate baseline release of CAR, providing initial preservation by Cu–pCDs. The presence of pectinase enhanced the release by degrading pectin-rich layers and partially disrupting the core–shell architecture, enabling enzyme-responsive release. Comprehensive characterization confirmed suitable mechanical performance (Tensile strength = 4.40 MPa; Elongation at break = 40.11%) and optimized water vapor barrier properties (Water vapor permeability = 9.10 × 10⁻⁷·m⁻¹·g⁻¹·h⁻¹·Pa⁻¹). Biphasic release behavior that depended on enzyme concentration was observed (<i>R</i>² ≥ 0.8733). Molecular docking indicated a favorable interaction (binding energy =  −&#xa0;5.9 kcal/mol). Under simulated packaging conditions, the pad effectively preserved color and firmness of broccoli, extending shelf life by three days. These findings demonstrate the potential of the pectin-gated nanofiber pad as an active packaging material for fresh produce.</p> Graphical Abstract <p></p>