An object of the present invention is to provide a piezoelectric stack substantially free from deterioration in performance and having high reliability, and a production method thereof. A piezoelectric layer 111, 112 comprising PZT and an internal electrode layer 121, 122 are alternately stacked; the grain boundary-filling factor of a Pb-based glass in the crystal grain boundary of the piezoelectric layer 111, 112 is 95% or more; in producing a piezoelectric stack 1 in which a piezoelectric layer 111, 112 comprising PZT and an internal electrode layer 121, 122 are alternately stacked, unfired sheets for the piezoelectric layer 111, 112 are stacked to produce an unfired stacked body, the unfired sheet containing Pb in excess of the stoichiometric ratio in PZT and having printed thereon an electrically conducting paste for the internal electrode layer 121, 122, and the unfired stacked body is fired in an oxygen atmosphere having an oxygen concentration of 40 to 100 vol % such that the grain boundary-filling factor of a Pb-based glass in the crystal grain boundary inside the piezoelectric layer 111, 112 is 95% or more.