Shotcrete is widely used in tunnels, bridges, culverts, and other large-scale projects. The accelerator is an additive employed to expedite the setting time of shotcrete. Previous research primarily concentrated on enhancing the early strength of accelerators, whereas their long-term stability has been inadequately investigated. In this study, pseudoboehmite (PB) and amorphous aluminum hydroxide (AAH) were incorporated into the accelerator to enhance its stability over a period of 90 days without any signs of crystallization or delamination. Furthermore, the accelerator exhibited an initial setting time of 170 s, a final setting time of 550 s, and a compressive strength of 11.58 MPa after 1 day. The mechanism of effects was studied by isothermal calorimetry, FTIR, XRD, TG-DTG, and SEM analysis. The enhancement in stability is attributed to the distinctive adsorption and thixotropic properties of PB, which facilitate the formation of an electrical double-layer structure in acidic solutions. The expedited setting and hardening are primarily due to the equilibrium between Al3+, SO42-, and Ca2+ ions, which accelerates the hydration process of cement. This research offers a methodology for developing a high-performance, alkali-free liquid accelerator.