The secondary aluminum ash is the black slag left after the primary aluminum ash is extracted from the metal aluminum. To address the environmental pollution and resource waste caused by the accumulation and landfill of aluminum ash, this study fabricated non-fired bricks by using secondary aluminum ash as the principal raw material, which was supplemented by cement, slaked lime, gypsum and engineering sand. The effects of mix proportions of various admixtures on the mechanical properties of non-fired bricks were investigated, and on this basis, the hydration mechanism was analyzed. The results showed that the mix proportions were 68.3% aluminum ash, 11.4% cement, 6.4% slaked lime, 4.2% gypsum and 9.7% engineering sand. The compressive strength of the fabricated bricks reached 22.19 MPa, and their quality indicators were in line with the MU20 requirements for Non-fired Rubbish Gangue Bricks. Evident hydration reaction occurred inside the non-fired bricks, with main products being calcium silicate hydrate (CSH), calcium aluminate hydrate (CAH) and ettringite (AFt). Besides, a dense structure was formed, which enhanced the brick strength.