Traditional pesticide formulations show poor utilization and environmental safety due to their low foliage adhesion and large auxiliaries. In this study, a novel and environment-friendly indoxacarb formulation was prepared to improve the pesticide’s utilization rate, target control characteristics and ecological security. Indoxacarb-loaded waterborne polyurethane–sodium alginate (PU/SA) nanoemulsions with film forming properties, alkaline responsive release, high effectiveness against Spodoptera litura, and reduced acute contact toxicity for nontarget organisms were successfully prepared. The colloidal properties, swelling and release behaviors, leaf adhesion, degradation dynamics and bioactivity assay of the indoxacarb-loaded PU/SA nanoemulsions were determined. Results showed that the obtained indoxacarb-loaded microcapsule particulates were approximately 57 nm in diameter, electronegative −45.9 mV, and uniformly dispersed in the nanoemulsions. The dried latex films of PU/SA in the alkaline environment revealed better responsive swelling and release characteristics than those in acidic and neutral conditions. Compared with a commercial emulsifiable concentrate, the indoxacarb-loaded PU/SA nanoemulsions were useful for the targeted control of S. litura, which have alkaline gut and showed reduced acute contact toxicity to Harmonia axyridia. Furthermore, the PU/SA formulation had better foliage adhesion and indicated the property of controlled-release and a persistent effect.