This paper is concerned with the kinetics of stibnite (Sb2S3) dissolution in H2SO4-NaCl-Fe(SO4)1.5-O2 solutions. The experimental results of our study showed a positive effect from ferric ions on stibnite dissolution of up to 0.05 M. An increase in H2SO4 concentration from 0.8 to 3 M and NaCl concentration from 0 to 3 M NaCl improved the stibnite dissolution. In solutions without ferric ions, the leaching occurs by the acid dissolution reaction producing H2S without forming elemental sulfur, as we confirmed by the X-ray diffraction (XRD) analysis of leach residues. In this case, the kinetic data was analyzed using a shrinking core model controlled by a chemical reaction, and the calculated activation energy was 54.6 kJ/mol. Conversely, in the presence of ferric ions, the XRD patterns of the leach residues showed large peaks for elemental sulfur, confirming that the stibnite was oxidized and formed a sulfur porous layer. The mechanism in the presence of ferric ions involved an acid dissolution reaction, with the diffusion of the reactant/product species through the porous product layer, followed by the oxidation of H2S by ferric ions. The kinetic data were analyzed using a diffusion-controlled model, and the activation energy was 123.8 kJ/mol. This high activation value is consistent with the proposed mechanism.