Spontaneous combustion gangue (SCG) is often used as aggregate in traditional cemented paste backfill (CPB) for mine backfill, but the activation of SCG is insufficient. To stimulate the activity of SCG for the preparation of spontaneous combustion gangue-granulated blast furnace slag backfill (SGB), a new CPB was prepared by activating SCG via a mechanochemical composite activation method and adding ground granulated blast furnace slag (GGBS) to improve its activity. The mixing ratio was optimized by the response surface method and satisfaction function, and the strength formation mechanism was analyzed by scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) and Fourier transform infrared spectroscopy (FTIR). The results showed that SCG had a certain pozzolanic activity, and the optimal grinding time was 30 min. The optimal mix ratio was 82.58% mass concentration, 2.93% alkali content, 30% GGBS content, and 52.92% fine gangue rate. Calcium silicate hydrate (C-S-H) gel and calcium aluminate sulfate hydrate (C-A-S-H) gel were the main reaction products of backfill, and with increasing curing age, C-S-H gel in the reaction system was gradually converted into C-A-S-H gel. FTIR analysis results showed that there were H-O-H, Si-O, and Si-O-T (T was Si or Al) bonds in the product, indicating that C-S-H gel and C-A-S-H gel were formed in the product. A new damage constitutive model was developed. The damage constitutive model could completely describe the backfill stress-strain curve. The study verified the feasibility of preparing cemented paste backfill with SCG and GGBS, which was beneficial to clean coal mine production and environmental protection.