This paper reports enhanced high-temperature piezoelectric properties of Bi(Zn0.5Ti0.5)O3-modified BiFeO3-BaTiO3 (BF–BT-xBZT) ceramics prepared by two-step sintering method. The resultant ceramics show a symmetrical transition from a rhombohedral–pseudo-cubic (R-PC) phase coexistence to main PC phase with the increase of x, whose R-PC fraction (CR/CPC) is 53.3/46.7, 52.9/47.1, 50.2/49.8, 27.4/72.6, 15.3/84.7 when x = 0, 0.005, 0.01, 0.03, 0.05, respectively. The modification of BZT inhibits the grain growth, reduces the leakage current and gradually drives ferroelectric to relaxor transition. Optimal piezoelectric properties: d33 = 193 pC N−1, Pr = 20.6 μC cm−2, TC = 503 °C and kp = 36% achieved at x = 0.01 composition, which is due to the synergistic effect of an appropriate CR/CPC ratio, improved insulation and good polarization performance. In addition, the depolarization temperature Td is close 280–312 °C, and the high-temperature d33 further increases to 286–347 pC N−1, which shows a good application prospect of lead-free piezoceramics at high temperature. Our work also confirms that the addition of (Zn0.5Ti0.5)3+ and two-step sintering method are an effective and convenient strategy to improve the high-temperature electrical performance of BiFeO3–BaTiO3 based lead-free ceramics.