Structuring oils using oleogels (OGs) represents a promising strategy for developing semi-solid lipid matrices with applications in food and other soft systems. This study evaluated the thermal stability and physicochemical properties of an oleogel (OG) formulated with extra virgin olive oil (EVOO) and beeswax (BW, 6%). The oleogel and olive oil samples were initially characterized by thermogravimetric analysis (TGA/DTG). The beeswax and oleogel samples were initially characterized by texture analysis. An antioxidant capacity (ORAC) analysis was initially applied to the beeswax sample. An initial rheometric analysis was applied to the oleogel sample. Fatty acid profiling and infrared spectroscopy were applied initially and finally to the oleogel and olive oil samples. During the thermal processing (80 °C, 14 days) of the oleogel and olive oil, analyses of the percentage of polar compounds, refractive index, and absorption parameters (K₂₃₂ and K₂₇₀) were performed. The oleogel exhibited a soft, pseudoplastic network, with lower hardness and mechanical strength than pure beeswax. Gelation modified the thermo-oxidative stability of EVOO, showing lower levels of polar compounds (from day 7 of heating; p = 0.028) and a slight delay in the onset of thermal degradation (Tonset), suggesting partial protection against the formation of polar degradation compounds. Furthermore, the evolution of K₂₃₂ indicated differences in the formation of primary oxidation products (p = 0.027) over the 14 days of heating, while K₂₇₀ showed no differences in the formation of secondary oxidation compounds. This reflects the complex interaction between the gelled matrix and the lipid deterioration mechanisms. Overall, the results demonstrate that the incorporation of beeswax allows for a partial reduction in degradation compounds in high-temperature processes, producing technologically functional oleogels that offer a potential alternative source for structuring solid fats. This work provides relevant evidence for the rational design of oleogels based on unrefined oils and opens new opportunities for their application in food systems and gelled matrices with thermal processing requirements.

Oleogelation represents a promising strategy for enhancing the functional and thermal properties of edible oils. This study evaluated the structural protection mechanism of an extra virgin olive oil (EVOO) oleogel, structured with 6% (w/w) beeswax, subjected to prolonged discontinuous deep-frying cycles compared to unstructured EVOO. Degradation kinetics were monitored through total polar compounds (TPCs), acid value, UV absorption, p-anisidine value, and FTIR-ATR spectroscopy. Structural integrity was evaluated via Texture Profile Analysis (TPA), and the thermal trajectory was modeled using Principal Component Analysis (PCA). The results explicitly demonstrate a two-stage kinetic behavior. During the initial phase (Days 1–3), the three-dimensional crystalline network acted as a steric confinement barrier, restricting molecular mobility and oxygen diffusion. This significantly delayed the formation of primary and secondary oxidation products, maintaining TPC and acidity markedly lower than the EVOO control. However, continuous thermal stress induced acute thermomechanical fatigue. By Day 4, the oleogel underwent severe structural collapse—evidenced by a 67% loss in hardness—which abolished the physical barrier and caused the degradation kinetics to accelerate, ultimately converging with those of the unstructured oil. These findings reveal that while beeswax oleogelation substantially boosts initial thermo-oxidative stability, its finite mechanical resistance limits its operational lifespan. Understanding this structural collapse is crucial for engineering more resilient, functionally tailored lipid matrices for high-temperature food applications.