The invention provides an alkali-free liquid quick-setting agent, a preparation method and applications thereof, wherein the raw materials comprise, by mass, 45-55% of aluminum sulfate, 5-10% of nanometer alumina, 5-10% of hydrofluoric acid, 3-7% of a solubilizing component, 2-6% of fluorosilicate, 1-4% of an early strength component, 0.5-1% of a stabilizer, and 20-32% of water. According to the present invention, the aluminum sulfate is used as the main raw material, and is matched with the nanometer alumina, the hydrofluoric acid, the solubilizing component, the fluorosilicate, the early strong component and the stabilizer, such that the obtained alkali-free liquid quick-setting agent has characteristics of good setting acceleration effect, long-term stability and low rebound rate, can substantially improve the earth strength of concrete, and can have high strength retention rate in late strength, wherein various performance indexes can meet the requirements on the first-class quick-setting agent in standard JC477-2005 Flash setting admixtures for shotcrete at a dosage of 7%.