This study investigated how acid concentration affects leaching from pyrolyzed LIBs’ (lithium-ion batteries’) black mass (BM) by stepwise acidification with eight acids at 70 °C under identical starting conditions. A citric-acid control without BM matched the calculated pH, whereas BM buffered solutions to ∼pH 9.5 and increased the measured pH. Stabilized pH provided a consistent reference within each experiment, but similar pH values across acids produced very different leaching efficiencies. At pH ≈ 3, lithium leaching was ∼pH 85% for formic acid and ∼pH 60% for citric acid. The maximum lithium leaching ranged from 49% (ascorbic acid) to 92% (sulfuric acid), while organic acids often showed limited cobalt and nickel dissolution. For formic acid, speciation and metal-formate solubility calculations showed that higher acid concentration does not necessarily increase transition-metal leaching and may suppress cobalt and nickel. Thus, pH is stable within each acid system but not transferable across acids, and high solid loading (250 g L⁻¹) further requires acid-specific evaluation. The results indicate that acid-dependent speciation and complexation, rather than proton concentration alone, control extraction and can decouple acid dosage from leaching performance.