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Stable primary emulsion formation in which different parameters such as viscosity and droplet size come into prominence for their characterization is a key factor in W/O/W emulsions. In this study, different emulsifiers (Crill™ 1, Crill™ 4, AMP, and PGPR) were studied to produce a casein-hydrolysate-loaded stable primary emulsion with lower viscosity and droplet size. Viscosity, electrical conductivity, particle size distribution, and emulsion stability were determined for three different dispersed phase ratios and three emulsifier concentrations. In 31 of the 36 examined emulsion systems, no electrical conductivity could be measured, indicating that appropriate emulsions were formed. While AMP-based emulsions showed non-Newtonian flow behaviors with high consistency coefficients, all PGPR-based emulsions and most of the Crill™-1- and -4-based ones were Newtonian fluids with relatively low viscosities (65.7–274.7 cP). The PGPR-based emulsions were stable for at least 5 days and had D(90) values lower than 2 µm, whereas Crill™-1- and -4-based emulsions had phase separation after 24 h and had minimum D(90) values of 6.8 µm. PGPR-based emulsions were found suitable and within PGPR-based emulsions, and the best formulation was determined by TOPSIS. Using 5% PGPR with a 25% dispersed phase ratio resulted in the highest relative closeness value. The results of this study showed that PGPR is a very effective emulsifier for stable casein-hydrolysate-loaded emulsion formations with low droplet size and viscosity.