The invention relates to a super-early-strength fluorine-free alkali-free liquid accelerator and a preparation method thereof. The accelerator is prepared from the following raw materials: aluminum sulfate, an organic dissolution promoter, a stabilizer, an early strength agent, a pH regulator and water. The organic dissolution promoter is formed by mixing a component A, a component B and a component C, wherein the component A is monoethanolamine, diethanolamine or triethanolamine; the component B is N-methyldiethanolamine, N,N-dimethylethanolamine or N,N-dimethylformamide; and the component C is diethylenetriamine, triethylene tetramine or tetrahydroxypropyl ethylenediamine. The stabilizer is selected from superfine sepiolite and pseudo-boehmite. The pH regulator is selected from p-toluenesulfonic acid, oxalic acid and formic acid. The early strength agent is selected from lithium sulfate, magnesium sulfate, nanometer silica sol and nanometer aluminum sol. The super-early-strength fluorine-free alkali-free liquid accelerator is good in performance, simple in preparation process, free of fluorine, alkali and chlorine and capable of meeting the performance requirements of various setting accelerator standards for alkali-free accelerators; and according to the liquid accelerator, compressive strength within 6 hours is far larger than 2.5 MPa, compressive strength within 1 day is far larger than 15.0 MPa, a compressive strength retention rate within 90 days is larger than or equal to 110%, and stability exceeds 9 months.