In recent decades, olive oil consumption has almost tripled worldwide. Olive oil production is linked with the production of enormous amounts of olive mill wastewater, the main by-product derived from three-phase olive mills. Due to the environmental risks of olive mill wastewater disposal, the management and valorization of the specific waste stream is of great importance. This work focuses on the thermophilic dark fermentation of olive mill wastewater in batch reactors, targeting pH optimization and the organic loading effect. A series of experiments were performed, during which the organic load of the substrate remained at 40 g/L after dilution with tap water, and the pH was tested in the range of 4.5 to 7.5. The maximum yield in terms of produced hydrogen was obtained at pH 6.0, and the yields were 0.7 mol H2/mol glucose or 0.5 L H2/Lreactor. At the same conditions, a reduction of 62% of the waste’s phenols was achieved. However, concerning the effect of organic loading at the optimized pH value (6.0), a further increase in the organic load minimized the hydrogen production, and the overall process was strongly inhibited.