BiFeO₃ thin films were prepared using the chemical solution route on Pt/TiO₂/SiO₂/Si(100) substrates under different crystallization kinetics. The crystallization kinetic effects on the dielectric and electrical properties have been investigated. These properties included dielectric permittivity, electric modulus, electrical conductivity measurements as a function of the temperature (300–525 K) and frequency (10²–10⁶ Hz), and leakage current measurements electric field range ± 30 kV/cm at room temperature. The differences observed in conductivity and current density of the BiFeO₃ films were discussed in terms of possible defects induced by the crystallization kinetic. An anomalous relaxor-like dielectric behavior characterized by a broad maximum in the real dielectric permittivity as a function of temperature and the low-frequency dielectric dispersion has been observed. The nonexpected peaks in the real permittivity were accompanied by increasing at least four orders in the conductivity’s magnitude at high temperatures. The origin of the relaxor-like dielectric anomalies is discussed, suggesting that the dielectric permittivity peaks are artifacts due to carrier migration correlated to the onset of the Maxwell–Wagner effect.BiFeO₃ thin films were prepared using the chemical solution route on Pt/TiO₂/SiO₂/Si(100) substrates under different crystallization kinetics. The crystallization kinetic effects on the dielectric and electrical properties have been investigated. These properties included dielectric permittivity, electric modulus, electrical conductivity measurements as a function of the temperature (300–525 K) and frequency (10²–10⁶ Hz), and leakage current measurements electric field range ± 30 kV/cm at room temperature. The differences observed in conductivity and current density of the BiFeO₃ films were discussed in terms of possible defects induced by the crystallization kinetic. An anomalous relaxor-like dielectric behavior characterized by a broad maximum in the real dielectric permittivity as a function of temperature and the low-frequency dielectric dispersion has been observed. The nonexpected peaks in the real permittivity were accompanied by increasing at least four orders in the conductivity’s magnitude at high temperatures. The origin of the relaxor-like dielectric anomalies is discussed, suggesting that the dielectric permittivity peaks are artifacts due to carrier migration correlated to the onset of the Maxwell–Wagner effect.