In this study, two types of biocarbons, namely CNCC and ACNCC, were developed by carbonization of corn cob (CNCC) and chemical activation of carbonization corn cob (ACNCC). CNCC and ACNCC were used as support materials mixed with composite phase change materials (cPCMs), respectively, by vacuum impregnation, which can not only prevent the leakage of cPCMs but also enhance its thermal conductivity. The measurement results showed that the specific surface area and pore volume of CNCC increased by 9.4 times and 6.4 times, respectively, after being activated. The cPCM was stably adsorbed into the pores of CNCC and ACNCC. The different components of the new shape-stable cPCMs have good chemical compatibility. Differential scanning calorimetry tests showed that the latent heat of two new cPCMs are 201.80 Jg-1 and 214.02 Jg-1, respectively. The thermal conductivity of two new cPCMs is 0.676 Wm-1 K-1 and 0.725 Wm-1 K-1, respectively. Furthermore, the new shape-stable cPCMs present remarkable chemical structural stability and thermal reliability after 150 heating/cooling cycles. This study provides a new type of hybrid PCM which has potential to be widely applied to heating, cooling and power industry, leading to the enhanced energy efficiency and reduced carbon emission globally.