The invention discloses a thermally stable lead-free high-temperature piezoelectric ceramic and a preparation method thereof, which is characterized in that the thermally stable lead-free high-temperature piezoelectric ceramic consists of components expressed by the following general formulas: (Naa Kb Lic Agd Bie) (Nbu Tay) O3 +xM1 +yM2, M1 is titanate of the following metals: Mg, Ca, Ba and Sr; M2 is the carbonate or oxide of the following metals: Na, K, Li, A1, Cu, Fe, Mn, Zn, Pr, Nd, Sm, Gd, La, Dy, Er, Yb, Sc and Sb; x and y are the percentages for which the weights of M1 and M2 account in the overall weight of raw materials. The lead-free high-temperature piezoelectric ceramic of the invention is a lead-free, environmentally coordinative, high-temperature piezoelectric ceramic with low agglomerating temperature, high curie temperature, stable thermal performance of electricity, and high mechanical strength, and has stable preparation technique and can be obtained by adopting the preparation technique and industrial materials for traditional piezoelectric ceramics, so the invention is practical.