The invention discloses an unleaded piezoelectric ceramic consisting of a B-site composite Bi-based compound and a preparation method thereof. The components of the unleaded piezoelectric ceramic are shown by the general formulae of (1-x) Bi (Li1 / 2Me1 / 2) O3 - xBaTiO3 + zMaOb, (1-x) Bi (Li1 / 2Me1 / 2)O3 - x (Na1 / 2Bi1 / 2)TiO3 + zMaOb, (1-x-y) Bi (Li1 / 2Me1 / 2) O3 - xBaTiO3 - y (Na1 / 2Bi1 / 2) TiO3 + zMaOb, (1-x-y) Bi (Li1 / 2Me1 / 2) O3 - xBaTiO3 - y (K1 / 2Bi1 / 2) TiO3, + zMaOb or (1-x-y-v) Bi (Li1 / 2Me1 / 2) O3 - xBaTiO3 - y (Na1 / 2Bi1 / 2) TiO3 - v(K1 / 2Bi1 / 2) TiO3 + zMaOb, wherein x, y, z and v denote mole fractions, 0 (x (1.0,0 (y (1,0 (v (1, 0< / = z< / =0.1, Me represents one or five pentavalent metallic elements, MaOb represents one or a plurality of oxides, M is an element of +1 to +6 valence, and can be formed into a solid oxide with oxygen, and the ceramic is prepared in a conventional ceramic preparation method. The prepared unleaded piezoelectric ceramic has a good sintering characteristic, the preparation process is simple and stable, the performance is excellent, and the unleaded piezoelectric ceramic can partially replace the conventional lead based piezoelectric ceramic to be used.