The effects of cooling rate on structure and multiferroic properties were investigated in the lead-free 0.67Sm(0.12)Bi(0.88)FeO(3)-0.33BaTiO(3) ceramics. Cooling in different medium induces the variations of phase fractions, c/a ratio and the distortion degree of oxygen octahedron, which can effectively regulate the multiferroic properties at room temperature. The high-temperature P4mm phase transforms to the Pm3m phase with the decrement of the cooling rate. The magnetoelectric coupling effect is nonlinearly related to the cooling rate, which is induced by the corresponding distortion in FeO6 octahedron. The ceramic cooled in water shows the largest remnant polarization of similar to 20.9 mu C/cm(2), while the ceramic cooled in furnace shows large remnant magnetization and magnetoelectric coupling coefficient of similar to 0.50 emu/g and 7.3 mV/(cmOe), respectively.