Polyglycerol polyricinolate (PGPR) and polyglycerol-2 dioleate were selected as model surfactants to construct water-in-oil (W/O) emulsions, and the effect of interfacial rheological properties of surfactant film on the stability of emulsions were investigated based on the interfacial dilatational rheological method. The hydrophobicity chain of PGPR is polyricinic acid condensed from ricinic acid, and that of polyglycerol-2 dioleate is oleic acid. Their dynamic interfacial tensions in 15 cycles of interfacial compression-expansion were determined. The interfacial dilatational viscoelasticity was analyzed by amplitude scanning in the range of 1–28% amplitude and frequency sweep in the range of 5–45 mHz under 2% amplitude. It was found that PGPR could quickly reach adsorption equilibrium and form interfacial film with higher interfacial dilatational viscoelastic modulus to resist the deformation of interfacial film caused by emulsion coalescence, due to its branched chain structure and longer hydrophobic chain, and the emulsion thus presented good stability. However, polyglycerol-2 dioleate with a straight chain structure had lower interfacial tension, and it failed to resist the interfacial disturbance caused by coalescence because of its lower interfacial dilatational viscoelastic modulus, and thus the emulsion was unstable. This study reveals profound understanding of the influence of branched structure of PGPR hydrophobic chain on the interfacial film properties and the emulsion stability, providing experimental reference and theoretical guidance for future design or improvement of surfactant.