Novel light-driven and electro-driven polyethylene glycol (PEG)/two-dimensional MXene composite (PEG@MXene) with enhanced thermal conductivity and electrical conductivity as form-stable phase change material (FSPCM) is first obtained via the simple vacuum impregnation by employing MXene as the supporting skeleton as well as thermally conductive and electrically conductive filler and PEG as the phase change working substance. Fourier transform infrared spectroscopy (FT-IR) indicates that no chemical reaction occurred between PEG and MXene during adsorption process, but X-ray diffraction (XRD) results show the crystalline regions of PEG was decreased by the incorporation of MXene. The differential scanning calorimetry (DSC), polarizing microscope (POM), as well as XRD results demonstrate that the MXene nanosheets act as heterogeneous crystal nuclei and promote the crystallization of PEG. The melting and freezing latent heats of PEG@MXene are as high as 131.2 and 129.5 J/g, respectively, the relative enthalpy efficiency is 80.3%, and the thermal conductivity and electrical conductivity are 2.052 W/mK and 10.41 S/m, respectively. The obtained PEG@MXene has excellent light-to-thermal conversion, electro-to-thermal conversion and thermal energy storage performance. All these results demonstrate that the obtained PEG@MXene will have a great potential application for thermal energy storage.