The current research presents an effective direct route to obtain high oil content zein-based emulsion gels at moderate temperatures that is feasible for large-scale production. The preparation procedure involved the dissolution of zein in 90% (w/w) aqueous ethanol, followed by addition of glycerol and oil, and finally heating at ~90 °C to induce ethanol evaporation which promotes zein self-assembly and aggregation. The CLSM and cryo-SEM images confirmed the formation of nanoscale spherical zein aggregates organized on the oil droplet interface while excess proteins form a continuous percolating network between the oil droplets. The coiled-coil conformation of zein particles and the role of hydrogen bonds leading to the formation of a zein network through association of spherical zein particles were confirmed using infra-red spectroscopy and temperature-dependent rheology, respectively. Hard gel (4 °C) to soft gel (90 °C) transition was observed in a temperature ramp rheology experiment, indicating strengthening and weakening of hydrogen interactions between the particulate protein aggregates. Similar hydrogen bond breakdown and reformation was observed in a thixotropy experiment while applying high shear and withdrawal, respectively. Stability studies revealed glycerol syneresis, resulting in the deterioration of the gel's mechanical properties due to increase in hardness and decrease in cohesiveness at room temperature. Overall, these results provide important insight into the gelation mechanism and gel characteristics of zein-stabilized emulsion gels prepared by a direct route under moderate temperature conditions, which can be used for various food applications.