The electric behaviors of both free-carbon phase and ceramic phase in polymer-derived amorphous silicoaluminum oxycarbide were studied by impedance spectroscopy. The results revealed that the resistance of both ceramic phase and free-carbon phase are similar to each other and decreased with pyrolysis temperature. Meanwhile, the ceramic phase showed higher capacitance than the free-carbon phase. With increasing pyrolysis temperature, the capacitance of the ceramic phase drastically decreased, but that of the free-carbon phase remained similar. Each phase exhibited a relaxation process, which moved to higher frequency with increasing pyrolysis temperature. The results are correlated with the structural evolution of the two phases.