The thermal and heat transfer characteristics of stearic acid during the solidification processes were investigated experimentally in a vertical annulus energy storage system. The temperature distribution and temperature variations with time at different radial positions during the freezing processes were obtained. The thermal characteristics of the stearic acid, including movement of the solid–liquid interface in the radial direction, and the effects of Reynolds number on the heat transfer parameters were studied. The heat flux was estimated by using a simple approximate model. A new copper fin was designed and fixed to the electrical heating rod to enhance the thermal conductivity of the stearic acid. The results show that the new fin can enhance both the conduction and the natural convection heat transfer of the PCM, and the enhancement factor during solidification is estimated to be as high as 250%. The effect of the fin width on the enhancement was also examined experimentally, and it is found that the fine fin usually produce more effective enhancement.