This study investigated the variance in adsorption behavior of polyglycerol emulsifiers at the oil- polyol interface and its consequential impact on emulsion properties and stability. The critical micelle concentration (CMCIFT), saturation adsorption capacity (Γ∞), and Langmuir constant (κ) of the emulsifier were determined through measurements of dynamic interfacial tension between glycerol and mineral oil with varying hydrophobic chains. Results indicated an increase in CMCIFT and hydrophobic chain length with an increase in the number of hydrophobic chains. Emulsifiers with differing initial particle sizes were synthesized, and the actual emulsifying area (SA), theoretical covering area (ST), and emulsifying index (EI) at the interface were calculated. Variations in coverage rate led to disparate adsorption behavior and arrangement of the emulsifier at the interface, thereby impacting emulsion stability. This study establishes a theoretical foundation for predicting the stability trend of polyol/oil (P/O) emulsions.