In this paper, the aluminum sulfate based alkali-free liquid accelerating agent was modified by fluorine silicon slag, and the performance index of alkali-free liquid accelerating agent modified by fluorine silicon slag was tested. XRD, TG-DTG and SEM were used to explore the action mechanism of aluminum sulfate base alkali-free liquid accelerating agent modified by fluorine silicon slag on cement hydration process. The results show that with the increase of fluorine silicon slag content, the rapid setting effect and strength of mortar increase first and then decrease. When the alkali-free liquid accelerating agent is modified by fluorine silicon slag, the appropriate content of fluorine silicon slag is 5.0% (mass fraction). At this time, the initial setting time is 1 min 20 s, the final setting time is 5 min 20 s, 1 d compressive strength is 13.8 MPa, and 28 d compressive strength is 52.4 MPa. Calcium silicate hydrate is formed by the reaction of silica in fluorine silicon slag and cement hydration product calcium hydroxide, which is beneficial to improve the early strength of cement. However, the process of cement hydration and hardening process is hindered by the reaction of fluorine and calcium hydroxide to produce a large amount of calcium fluoride precipitation.