Using a diamond anvil cell, the evolutions of alternate-current impedance spectra and direct- current resistivity in B12As2 have been investigated up to 51.9 GPa. The results provide evidence for the existence of grain and grain boundary effects that are separated in the frequency region. The grain boundary resistance shows a relatively smaller contribution to the total resistance above 16.8 GPa. By using the double-Schottky barrier model, the space charge potential was obtained. A pressure-induced inversion of charge defect concentration in the space charge layer was found at 20.7 GPa. The high-temperature resistivity measurements indicate that the transport activation energy is determined by defect energy levels in the band gap.