A series of liquid and photoliquefiable azobenzene (Azo) derivatives (Azo-Cn-Br) have been synthesized for molecular solar thermal fuels. Each of the liquid and photoliquefiable azo derivatives shows a high degree of isomerization, a fast isomerization rate, a long half-life, an appropriate energy storage density, and a solvent-free “charging” and “discharging” process. The photoliquefied azo derivatives can isomerize upon UV light irradiation at low temperatures to give the “UV-charged” azo ones. Therefore, the phase transition enthalpy is stored simultaneously along with the isomerization enthalpy. The “UV-charged” azo derivatives are capable of releasing heat under the manipulation of blue light.