Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage (AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, environmentally friendly material in wastewater treatment. Unstable schwertmannite is prone to recrystallization. Understanding the mechanisms that induce schwertmannite labilization and affect its capacity to remove heavy metals are of great environmental and geochemical significance. Thiocyanate (SCNˉ) is a hazardous pseudohalide that is also normally found in AMD. However, little is known about the impact of Fe(III)-binding ligand SCNˉ on schwertmannite stability and its subsequent capacity to bind trace elements. Here, we investigated the adsorption of SCNˉ on schwertmannite and subsequent mineral transformation to characterize this little-known process. The appearance of Fe2+ indicated that the interactions between schwertmannite and SCNˉ may involve complexation and reduction reactions. Results showed that the majority of the adsorbed-SCNˉ was immobilized on schwertmannite during the 60-days transformation. The transformation rates of schwertmannite increased with increasing concentrations of SCNˉ. Goethite was detected as the dominant transformation product with or without SCNˉ. The mechanisms of SCNˉ-promoted dissolution of schwertmannite can be described as follows: (1) formation of Fe (III)-NCS complexes on the schwertmannite surface and in solution, a process which increases the reactivity of solid phase Fe(III); (2) the extraction of Fe(III) from schwertmannite by SCNˉ and subsequent schwertmannite dissolution; and (3) the formation of secondary minerals from extracted Fe(III). These findings may improve AMD treatment strategies and provide insight into the use and potential reuse of schwertmannite as a trace element sorbent.