The invention discloses a novel perovskite structure high-entropy ceramic and a preparation method thereof. The structure of the ceramic is an ABO3 type perovskite structure, the A-site element is Sr, and the B-site element is Zr, Hf, Ce, Yb and Me which are in an equal molar ratio. The preparation method comprises the following steps: putting the components into a mortar, adding absolute ethyl alcohol, and performing grinding; performing drying in a drying oven after the grinding, then transferring dried material into a muffle furnace for pre-calcining, and naturally cooling obtained material to room temperature to obtain a ceramic powder; putting the ceramic powder into the mortar, adding a polyvinyl alcohol aqueous solution and absolute ethyl alcohol, performing grinding again, and performing drying and sieving after the grinding is sufficient, adding the sieved ceramic powder into a steel mold of a table type powder tablet press, pre-pressing into a disc-shaped or strip-shaped block material, and then putting the block material into a cold isostatic press for cold isostatic pressing treatment to obtain a ceramic green body; and finally, calcining the ceramic green body in a muffle furnace, and performing cooling in the furnace to obtain the novel perovskite structure high-entropy ceramic. The high-entropy ceramic has the advantages of high stability, low thermal conductivity and relatively high hardness and density.