In the pursuit of reducing oil separation in peanut butter, oleogels synthesized from diacylglycerol (DAG)-rich peanut oils, using glycerol monostearate (GMS) as the gelator, were examined as alternative stabilizers. In comparison to triacylglycerol (TAG)-rich peanut oils, the DAG oil-based oleogels exhibited better oil-binding capacities across increasing GMS concentrations. Intriguingly, thermal and rheological assessments pointed to a weaker network structure in DAG oil oleogels, as evidenced by their lower crystallization temperatures and reduced viscoelastic parameters (G' and G''). Insight from infrared spectroscopy revealed that this could stem from heightened intermolecular hydrogen bonding between the DAG oil and the gelator. When applied to peanut butter, DAG oil oleogels demonstrated efficacy in minimizing oil separation. Extended storage trials affirmed the long-term stability of peanut butter formulations incorporating these oleogels. Furthermore, sensory evaluations by panelists underscored favorable impressions, suggesting potential consumer acceptance. Overall, this study illuminates the promising role of DAG oleogels as effective, alternative stabilizers in peanut butter formulations.