Noninterface-active polysaccharides can acquire better emulsifying properties through microgelation, yet optimizing their emulsifying performance remains a significant challenge. This study introduces a novel approach to enhance the emulsifying performance of polysaccharide microgels by leveraging the cross-interfacial diffusion of polyphenols, which promotes the interfacial adsorption of microgels. Tannic acid (TA) was predispersed in oil phases and subsequently emulsified with agarose microgel (AM) suspensions, and the impacts of TA diffusion on the emulsifying performance of AMs was investigated. In addition, the transmittance profiles of oil-water biphasic systems were found to innovatively indicate the cross-interfacial diffusion of TA and the interfacial adsorption of AMs. The current results suggest that an appropriate level of TA incorporation can benefit the emulsifying performance of AMs, correlating with decreased droplet sizes and improved physical stability of the emulsion. However, excessive TA might trigger the clustering of AMs before they reach the interfacial layer, adversely affecting the emulsion stability. In conclusion, the cross-interfacial diffusion of polyphenols offers a promising strategy to overcome the stability challenges encountered in polysaccharide microgel-stabilized emulsions.