In this paper, we investigate the release of heavy metals from sludge produced from an electrical industry using both organic and inorganic acids. Single and sequential extractions were conducted to assess heavy metals in different phases of the sludge. Metal release from sludge was investigated in the presence of three inorganic acids (nitric, sulfuric, and phosphoric) and three organic acids (acetic, malic, and citric) at concentrations ranging from 0.1 to 2.0 mol L−1. Sequential extraction indicated the presence of Cu primarily in the carbonate fraction, Pb in the residual fraction, and Ni in the Fe[sbnd]Mn oxide fraction. The cumulative release rates of heavy metals (i.e., Pb, Cu, and Ni) by 1.0 mol L−1 of acid increased with the use of the following acids in the order of: malic < sulfuric < acetic < phosphoric < citric < nitric. Acetic acid exhibited the highest release of Cu, at a rate of 72.62 × 10−11 mol m−2 s−1 at pH 1, and malic acid drove the release of Pb at a maximum rate of 3.90 × 10−11 mol m−2 s−1. Meanwhile, nitric acid provided the maximum rate of Ni release (0.23 × 10−11 mol m−2 s−1) at pH 1. The high rate of metal release by organic acids is explained through ligand-promoted mechanisms that enhance the release of metal ions from the sludge. The results from our study emphasize that an understanding of the metal release mechanism is key to selecting the optimal acid for the maximum recovery of heavy metals.