Porous high internal phase emulsion templated polymers (PHPs) with/without carbon nanofiber (CNF) frame-works were synthesized for shape-stabilization of hexadecanol (HD) selected as phase change material (PCM) for thermal energy storage (TES) applications. This impregnation process was resulted in creation of seepage-free composite PCMs with high latent heat storage (LHS) capacity and enhanced thermal conductivity. Morphology, chemical structure, LHS properties and thermal stability of prepared composites were characterized by SEM, FT-IR, DSC and TGA techniques. DSC analysis indicated that the PHP/HD and PHP@CNF/HD(80wt%) composites have a LHS capacity of over 200 J/g at about 46-47 degrees C. The cycled-composite PCMs showed outstanding thermal reliability and chemical stability. Thermal decomposition temperature of HD was considerably extended after impregnation with PHP and PHP/CNF scaffolds. Thermal conductivity of PHP/HD and PHP@CNF/HD was enhanced compared to that of pure HD. The reduction in heat storing/releasing times of PHP@CNF/HD composites relative to PHP/HD composite was proved by considering the measured temperature-time change. Accordingly, especially PHP@CNF/HD composites PCMs have promising prospective for medium temperature-TES practices.