Secondary aluminum dross (SAD) is an inevitable by-product from the secondary aluminum industry and has caused serious environmental issues. In this study, the effect of pretreatment operations on the subsequent acid leaching operation was studied by process mineralogy, a series of leaching experiments, XRD, and SEM. Leaching results showed that the leaching efficiency of Al in direct acid leaching was only 22.99%. Process mineralogy showed the complex intertexture and continuous network structure in the SAD. Pretreatment operations were extremely efficient in destroying the structure by physical and chemical interaction. Interestingly, by adding the grinding and water leaching operations, the leaching efficiency of total aluminum in the SAD reached approximately 28.70%. XRD results showed that nearly all metallic Al, AlN, and partial Al2O3 were leached by grinding−water leaching−acid leaching. The scanning electron micrographs showed that the residue particles mainly included some insoluble components and had a smooth surface.