Avermectin (AVM) is a highly effective and safe biopesticide but is very sensitive to ultraviolet (UV) light and exhibits poor water solubility. Developing green and multifunctional adjuvants is important for the protection and controlled release of AVM. In this work, a number of water-soluble enzymatic hydrolysis lignins (W-EHLs) were prepared via grafting basic amino acids and used as emulsifiers with co-surfactants to prepare high-internal phase emulsions (HIPEs). The results showed that W-EHLs with co-surfactants could be prepared with HIPEs that contained 90 vol % green oil phases such as turpentine, and the stability of the HIPEs first increased and then decreased when the rate of grafting of basic amino acids on lignin increased from 0.26 to 1.46 mmol/g. The more polar oil droplets were less deformable due to their higher viscosity, thereby affording a stability advantage to HIPEs. Subsequently, the relations between the stability and interfacial viscoelasticity of the emulsion were effectively correlated by interfacial rheology, droplet size, and physical stability tests. The results showed that HIPEs with smaller droplets had poor fluidity and strong interfacial viscoelasticity due to their higher droplet packing density, which resulted in good macroscopic stability. Like the AVM carrier, the retention rate of AVM in HIPEs was 80.1% after UV radiation for 72 h, which represented the highest UV protection efficiency in AVM delivery systems. The release curves showed that the rate of release of AVM from HIPEs was adjusted by controlling the pH value of the medium. In addition, the release of HIPEs is completely in accord with both diffusion and the matrix erosion mechanism. The strategy could be extended to other sensitive pesticides and used to promote the development of sustainable agriculture.