Direct current (DC) electrical performances of crosslinked polyethylene (XLPE) have been evidently improved by developing graft modification technique with ultraviolet (UV) photon-initiation. Maleic anhydride (MAH) molecules with characteristic cyclic anhydride were successfully grafted to polyethylene molecules under UV irradiation, which can be efficiently realized in industrial cable production. The complying laws of electrical current varying with electric field and the Weibull statistics of dielectric breakdown strength at altered temperature for cable operation were analyzed to study the underlying mechanism of improving electrical insulation performances. Compared with pure XLPE, the appreciably decreased electrical conductivity and enhanced breakdown strength were achieved in XLPE-graft-MAH. The critical electric fields of the electrical conduction altering from ohm conductance to trap-limited mechanism significantly decrease with the increased testing temperature, which, however, can be remarkably raised by grafting MAH. At elevated temperatures, the dominant carrier transport mechanism of pure XLPE alters from Poole–Frenkel effect to Schottky injection, while and XLPE-graft-MAH materials persist in the electrical conductance dominated by Poole–Frenkel effect. The polar group of grafted MAH renders deep traps for charge carriers in XLPE-graft-MAH, and accordingly elevate the charge injection barrier and reduce charge mobility, resulting in the suppression of DC electrical conductance and the remarkable amelioration of insulation strength. The well agreement of experimental results with the quantum mechanics calculations suggests a prospective strategy of UV initiation for polar-molecule-grafting modification in the development of high-voltage DC cable materials.