The present invention provides a fly ash-based environmentally-friendly hydrogel with a high water retention for preventing and controlling spontaneous combustion of coal in a mine and a preparation method thereof. The hydrogel includes the following raw materials in the following weight percentages: 10% to 30% of a gel-forming material A, 20% to 45% of a crosslinking material B, and water as a balance, where the gel-forming material A is prepared by physical blending of a biodegradable superabsorbent resin, anionic polyacrylamide, a sesbania gum, and fly ash in a weight ratio of (1-3):(0.5-1):(0.5-1):(95-98); and the crosslinking material B is prepared by subjecting zeolite, expandable graphite, and an aluminum citrate complex in a weight ratio of (60-78):(20-36):(2-4) to mixing, dispersing, adsorbing, and freeze-drying. The gel-forming material A is added to water and stirred at room temperature until homogeneous, and then the crosslinking material B is added and stirred until homogeneous to obtain the hydrogel. In the present disclosure, the environmentally-friendly hydrogel with the high water retention is prepared with wastes such as fly ash as a base material, and can be prepared simply with a low cost. In addition, the hydrogel has the advantages of degradability, strong water retention, and a controllable gelation time. The hydrogel can cover and wet a coal body for a long time, and prevent and control the spontaneous combustion of coal in a mine for a prolonged time.