Secondary aluminum dross (SAD) contains large amounts of toxic components (AlN, fluoride, and chloride salts), which limits its large-scale utilization. Problems such as high acid or alkali usage and high liquid–solid ratio make it difficult to industrialize the disposal of SAD. In the previous study, authors achieved self-driven hydrolysis of SAD, and the double-edged effects of Na/K aluminosilicates generation on denitrification and desalination during the leaching process of SAD were also revealed. Based on this, a new approach for simultaneous denitrification, desalination, and fluoride fixation of SAD by calcium-driven hydrolysis was proposed in this study. Thermodynamic analysis indicated that calcium aluminosilicates are more easily precipitated than sodium and potassium aluminosilicates in solution. Kinetic analysis showed that the denitrification reaction was controlled by a mixture of chemical reaction and diffusion, the dissolution of Al(OH)3 inclusions to Al(OH)4- was the limiting link. Mechanistic analysis revealed that Ca2+ replaced Na+ and K+ and preferentially reacted with Al(OH)4- and H3SiO4- to form calcium aluminosilicates, which promoted the removal of Na and K. Calcium aluminosilicates exhibited a greater ability to promote the dissolution of Al(OH)4- than sodium and potassium aluminosilicates, which further enhanced denitrification. As a bonus, Ca2+ also realized the fixation of soluble F-. Under the optimal conditions (L/S=1.5, T=80 ℃, t = 300 min, CaCl2(wt.%) = 10%), the denitrification rate was increased to 91.12%, Na and K contents were reduced to 0.24 wt% and 0.14 wt%, respectively, the removal of Cl was 99.30%, and the fixation rate of F was 99.00%.