The invention discloses a self-lubricating non-stick molten aluminum environment-friendly coating, a coating film and a preparation method of the self-lubricating non-stick molten aluminum environment-friendly coating. The preparation method comprises the following steps of mixing a silane coupling agent containing amino or epoxy groups, deionized water and tetramethylammonium hydroxide, and carrying out ultrasonic dispersion and hydrolysis to prepare a polysiloxane oligomer aqueous solution I; conducting stirring continuously, and sequentially adding dipropylene glycol butyl ether, boron nitride, talcum powder, low-temperature glass powder and Al2O3 for dispersing; adding gas-phase SiO2 for dispersing so as to prepare water-based slurry II; and mixing the polysiloxane oligomer aqueous solution I and the slurry II, and carrying out ultrasonic dispersion to prepare the self-lubricating non-stick molten aluminum environment-friendly coating. The coating film prepared from the coating hasthe advantages of stability, reliability, no toxicity, no powder falling, cracking, discoloration and gasification on the surface at 800 DEG C, self-lubricating property, no adhesion of molten aluminum, capability of being used as an environment-friendly, clean and efficient release agent for cast aluminum, the simple preparation process, convenience in construction, environmental friendliness and the like.