A hydrogel film with pH-responsive release and excellent antibacterial properties was developed by utilizing mesoporous silica nanoparticles (MSNs) as carriers for ε-PL. Carboxymethyl chitosan (CMCS) is grafted onto aminated-MSNs through amine-bond reaction mediated, which is subsequently bound to polyvinyl alcohol (PVA) by esterification reaction. The addition of MSNs and optimization of CMCS proportion improved the dispersion stability of CMCS/PVA, resulting in a TSI value of 0.6 for 1.6CMCS/0.8PVA@MSNs-ε-PL, which is significantly lower than other groups. The proportion increase of CMCS improved the thermal stability and water oxygen barrier capacities of the 1.6CMCS/0.8PVA@MSNs-ε-PL by enhancing cross-linking with MSNs. The 1.6CMCS/0.8PVA@MSNs-ε-PL exhibited pH-responsive release behavior, with the extent of release increasing proportionally with higher pH levels. The 1.6CMCS/0.8PVA@MSNs-ε-PL exhibited significant antibacterial activity against Pseudomonas azotoformans MN10 in vitro, attributed to the ε-PL's ability to damage the bacterial membrane structure. Hence, the 1.6CMCS/0.8PVA@MSNs-ε-PL exhibits significant potential in food preservation.