A lead-free piezoelectric ceramic composition wherein a suitable amount of Cu is contained in a perovskite compound of a non-stoichiometric composition represented by a formula (KxA1-x)y(Nb1-zBz)O3, wherein “A” represents at least one of Na and Bi, while “B” represents at least one of Ta and Ti, and wherein 0<x≦1, 0<y<1, and 0≦z≦1, so that by-products such as KaCubNbcOd and KaCubTacOd are produced as a result of reaction of (Nb1-zBz) with Cu in the process of calcination of a starting material, and the by-products restrict melting and abnormal grain growth of (KxNa1-x)(Nb1-zTaz) O3 during firing of a calcined body, thereby improving sinterability of the fired body, while restricting volatilization of alkali components and melting of KNbO3, thereby increasing the density and improving the piezoelectric properties of the fired body. The ceramic composition is prepared by firing a starting composition including the perovskite composition as a primary component, and a secondary component in the form of at least one of compounds KaCubNbcOd, KeCufTagOh and KiCujTikOl.