High-performance alkali-free accelerators require a mechanistic understanding of interactions between inorganic accelerants and organic modifiers. Although aluminum sulfate (AS) promotes rapid ettringite (AFt) formation, uncontrolled crystallization leads to coarse microstructures and instability from AFt-to-AFm conversion. Here, a molecular-scale synergistic mechanism is identified in which an amide regulates AS-driven hydration. The amide controls nucleation and growth of AFt and C–S–H via chemisorption on C₃A/C₃S and complexation with Ca²⁺. Within the tested mixing proportions, the high-aluminum-sulfate and moderate-amide combination achieves the highest early strength (17.05 MPa at 1 day) via constructing an interlocked AFt/C–S–H skeleton, whereas excessive amide suppresses crystallization and low AS accelerates AFt-to-AFm conversion, reducing long-term performance. In-situ XRD, thermal analysis, and microscopy confirm a denser, more stable microstructure (27.37 MPa at 10 days) with minimal 28-day strength loss (17.38 MPa). Density functional theory shows an adsorption hierarchy of amide > AS species > H₂O, explaining its dominant surface-modifying role. This study provides a framework for designing cement accelerators with balanced early strength and durability.