This paper presents the influence of three different voltage stabilizers, 4-n-propylbenzoic acid, 2-methoxyphenylboronic acid, and 3-aminobenzoylmethylamide, on the insulation properties of cross-linked polyethylene (XLPE). The 1 wt % voltage stabilizers are blended with XLPE by a solution method, and then the samples are prepared via a hot pressing method. Electrical and physicochemical properties of the XLPE blends are analyzed by space charge, DC resistivity, DC breakdown strength, thermally stimulated depolarization current, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry experiments. It is found that the addition of the voltage stabilizers enhances the DC resistivity and DC breakdown strength of the XLPE, which also inhibits the accumulation of space charges in the XLPE. The results show that the XLPE blend with the addition of 4-n-propylbenzoic acid has the lowest conduction current and a 23.3% increment in the DC breakdown strength compared to that of the reference XLPE among the used voltage stabilizers. Moreover, it is found that the melting properties and thermal stability of the XLPE are not affected by the addition of the voltage stabilizers. The XLPE blend with 4-n-propylbenzoic acid exhibits a uniform trap depth distribution, which facilitates the migration of the space charge to the anode and reduces the electric field inside the sample bulk. Quantum chemical calculations demonstrate that the matching ability of the electron-withdrawing and electron-donating groups of the three voltage stabilizers effectively enhances the electrical properties of the XLPE. In contrast, the 4-n-propylbenzoic acid has the lowest unoccupied molecular orbital energy level, which can effectively buffer the high-energy electrons and increase the DC breakdown strength. A charge carrier transport mechanism is also proposed to explain the effect of the voltage stabilizer on the space charge movement in the tested samples.