The optimal proportion of alkali-activated steel slag–slag cementitious materials is investigated by considering the combined effects of steel slag content, alkali content, water glass modulus, and water–binder ratio using the Box–Behnken design in response surface methodology. Qualitative and semi-quantitative analyses of X-ray diffraction (XRD) patterns and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS) images are conducted. The microstructural mechanism is elucidated based on the chemical composition, surface morphology, and microscale pore (crack) structures of the samples. A microreaction model for the alkali-activated steel slag and slag is proposed. The optimal composition for alkali-activated steel slag–slag cementitious materials is as follows: steel slag content, 38.60%; alkali content, 6.35%; water glass modulus, 1.23; and water–binder ratio, 0.48. The strength values predicted by the response surface model are p1d = 32.66 MPa, p7d = 50.46 MPa, and p28d = 56.87 MPa. XRD analysis confirms that the compressive strength of the sample is not only influenced by the amount of gel formed, but also, to a certain extent, by the CaCO3 crystals present in the steel slag, which act as nucleation sites. The SEM-EDS results confirm that the gel phase within the system comprises a hydrated calcium silicate gel formed through the reaction of volcanic ash and geopolymer gel formed through geo-polymerization. Analysis of the pore (crack) structure reveals that the compressive strength of the specimens is primarily influenced by porosity, with a secondary influence of the pore fractal dimension.