To improve the energy utilization efficiency of solar energy, Ti4O7/PEG/SiO2 form-stable phase change material (PCM) with characters of light-heat conversion and thermal conductivity enhancement was developed by in-situ doping titanium black (Ti4O7) through acid and alkali catalytic sol-gel method. The structure and properties of PCM were investigated by SEM, FT-IR, XRD, DSC, TG, coefficient of thermal conductivity and thermal conversion testing, etc. The results showed that the Ti4O7/PEG/SiO2 could effectively absorb UV visible light of solar radiation, simultaneously, the light energy was translated into thermal energy which was storied by PCM. Furthermore, the composite PCM exhibited good thermal stability below 360 degrees C, excellent shape-stabilized effect and high thermal conductivity. The Ti4O7/PEG/SiO2 as novel thermal storage material can usefully enhance the utilization efficiency of solar energy.