The invention discloses a preparation method of an environment-friendly autoclaved aerated concrete block. The method comprises the following steps: mixing and grinding a ceramic waste, loess, quicklime and desulfurized gypsum, and feeding the mixture into a sintering machine to obtain mixed aggregates; feeding methyl acrylate, ethylene oxide and an Al/Mg/Ce inorganic salt composite catalyst into a sealed reactor, carrying out heating, stirring, standing and cooling under nitrogen protection, adding rosin, phenol, sodium polynaphthalene sulfonate and concentrated sulfuric acid for mixing, and carrying out heating and stirring; sequentially adding sodium hydroxide and water for stirring to obtain a foaming agent; adding powdery sodium silicate, calcium lignosulphonate and anhydrous sodium sulfate to the mixed aggregates for ball-milling, and adding cement, polyvinyl alcohol and the foaming agent for stirring to obtain mixed slurry; and casting the mixed slurry into a mold for molding, and carrying out heating, pre-curing, demolding, cutting, autoclaved curing and cooling to obtain the environment-friendly autoclaved aerated concrete block.