The aligned CNT-based composite in transverse direction to the alignment is considered as completely insulating and unsuitable for utilization in de-icing system. Here, we have found that the aligned CNT-based composite in transverse direction to the alignment exhibited excellent electrothermal performance at high voltage, for the first time. Furthermore, we compared and investigated the electrical and electrothermal performance of the aligned and random non-percolative CNT/crosslinked polyethylene (XLPE) composites at high voltage. A temperature increase of 7.5–72.7 ℃ at a record high voltage of 900–3100 V is reached for the aligned CNT/XLPE composites. The filed emission at high voltage enables the electron to transfer along the CNTs radial direction, resulting in joule heating for the aligned CNT/XLPE composites in transverse direction to the alignment. Besides, the non-percolative structure contributes a temperature increase of 8.2–40.1 ℃ at a applied voltage of 900–2800 V to random CNT/XLPE composites. The high applied voltages is significantly higher than rGO-based composites. More importantly, effective de-icing and anti-icing performance at high voltage of 900–2800 V are achieved for the random non-percolative and aligned CNT-based composites at −20 ℃. These results demonstrate the potential of applying the CNT/XLPE composites in de/anti-icing system of transmission-lines and other fields requiring joule heating at high voltage.