Exploring new sources of natural antioxidants is of great interest to edible oil producers, in line with the toxicological problems generated by the use of synthetic antioxidants. This study assesses the potential of lyophilized Pinot Noir grape pomace extract (GPE) to enhance the sunflower oil stability against thermo-oxidative damage compared to BHT during a prolonged exposure to convective heat at 185 °C. Oil thermo-oxidation was monitored based on specific indices such as peroxide value (PV), para-anisidine value (p-AV), inhibition of oil oxidation (IO), total oxidation (TOTOX) value, conjugated dienes and trienes (CDs, CTs), but also by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), where absorbance ratios A 3009 cm−1/A 2922 cm−1 (RI), A 3009 cm−1/A 2853 cm−1 (RII), A 3009 cm−1/A 1744 cm−1 (RIII) and RIV = A 1744 cm−1/A 2922 cm−1 (RIV) were investigated. GPE showed a significant inhibitory effect on oil thermo-oxidation and this response was concentration-dependent. Substantial decreases in the investigated indices, compared to the control without added antioxidants, were obtained after 4 h and 8 h of heat exposure of the 800 ppm GPE sample: PV (47%; 42%), p-AV (38%; 33%), IO (54%; 46%), TOTOX (41%; 37%), CDs (46%; 39%), CTs (44%; 29%). Oil exposure to heat resulted in changes in RI–RIV attributed to the reduction in the degree of unsaturation, in response to primary and secondary lipid oxidation. FTIR spectroscopy can be used to differentiate untreated and heat-treated oils based on the absorbance ratios. An inhibitory effect close to that of BHT was achieved by 500 ppm GPE, while a dose of 800 ppm provided greater protection against thermo-oxidation. Our results promote GPE as a natural additive to limit the thermo-oxidative damage of plant oils.