Microstructure and dielectric behaviors of heating/cooling and bias-field were investigated in lead-free ceramics ([Formula: see text])[Formula: see text][Formula: see text][Formula: see text]BaTiO3 (BNT[Formula: see text]BT, [Formula: see text], 0.02, 0.04, 0.06, 0.08 and 0.10). The relaxor characters and the Vogel–Fulcher law of frequency-dependent dielectric properties were analyzed. Three dielectric anomalies with pronounced frequency dispersion at [Formula: see text], a maximum dielectric with variable frequency-dispersion at [Formula: see text] and a third Maxwell–Wagner-type relaxation over a wide temperature range in high-temperature region were observed. The significant dielectric thermal hysteresis, low barrier energy, high freezing temperature in heating process and the maximum dielectric tunability appeared in [Formula: see text] ceramic.