To further understand redox mechanisms occurring in wine, caffeic acid (CAF, 150 mg/L) and/or glutathione (GSH, 150 mg/L) were added to a model wine solution, followed by ferric iron (2 mg/L Fe(III), added as 10 mg/L Fe(III) chloride hexahydrate), while monitoring the oxidation–reduction potential (ORP, redox potential). Caffeic acid produced only modest ORP changes. In contrast, glutathione and caffeic acid + glutathione additions dropped the ORP from 243 mV and 238 mV, respectively, to the same post-addition value of 189 mV, suggesting that glutathione dictated the ORP, while caffeic acid showed no effect. The quinone of caffeic acid (assumed as changes in AU at 420 nm), was not detected, suggesting caffeic acid did not participate in oxidation reactions under wine conditions under superfluous amounts of dissolved oxygen (DO). After the addition of Fe(III), ORP increased to similar values across all treatments: 266 mV (FE), 269 mV (CAF), 284 mV (GSH), and 242 mV (CAF + GSH), suggesting that the Fe(II)/Fe(III) redox couple dominated the ORP electrode response. CAF + GSH produced the steepest ORP decline after the addition of Fe(III) chloride hexahydrate (β (slope of the ORP) = −0.7082), significantly steeper than FE (β = −0.3051; p = 0.0032) and GSH (β = −0.4643; p = 0.0496), suggesting synergistic radical quenching and metal redox cycling. Photo-Fenton-like reactions likely contributed to slight decreases in the ORP over time. In conclusion, glutathione strongly lowered the ORP, Fe(III) increased the ORP across treatments, and caffeic acid had minimal impact on the ORP under model wine conditions.