Nanostructured carbon materials possessing good mechanical properties, adsorption characteristics and electrochemical performances, are the most promising candidate for electrode materials of supercapacitors. Among all synthesis methods, hydrothermal synthesis of porous carbon nanosphere (PCNS) is mostly used. Structure-directing agent F108 (PEO132-PPO50-PEO132) has a similar function to popular agent F127(PEO106-PPO70-PEO106) and P123 (PEO20-PPO70-PEO20) used in hydrothermal synthesis, but has greater relative molecular mass and higher hydrophilic/hydrophobic volume ratio, so using block copolymer F108 as soft template will obtain PCNS with special physicochemical properties. In this paper, PCNS is prepared by post-processing, including carbonization and subsequent KOH activation, of phenolic resin nanoparticles obtained by hydrothermal synthesis through using phenolic resin as a carbon source and block copolymer F108 as a soft template. The as-prepared PCNS sample is characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction, nitrogen adsorption and FTIR, etc. The images of SEM, TEM and results of nitrogen adsorption show that the obtained PCNS has the advantages, such as uniform particle size about 120 nm, high spherical degree and large specific surface area of 1403 m2/g and also wide pore size distribution. The results show that post-processing has an important influence on the physicochemical property of PCNS sample such as specific surface area, pore size distribution, crystallinity and surface chemistry. The activation temperature plays an important role in forming pore structure as the specific area of PCNS sample increases from 519 m2g-1 to 1008 m2g-1 after activation at 700℃ (PCNS700), while the activation temperature changes to 900℃ (PCNS900), the specific area rises up to 1403 m2g-1. The pore size distributions show that the peaks are at the same position, which suggests that KOH activation at high temperature makes the primary pore of PCNS deeper. PCNS900 contains more mesopores than PCNS700, so it can be concluded that at the higher activation temperature, the deeper pores inside PCNS are formed, and it is worth noting that pores near 2 nm are largely produced when the temperature arrives at 900℃. KOH processing and high temperature processing contribute greatly to structural ordering, which means that PCNS samples are greatly graphitized. Last but not least, both KOH processing and high temperature processing reduce the number of functional groups on the surface of PCNS samples. Using PCNS samples as activated material to make electrodes, we study how the different physicochemical properties of PCNS samples affect the performance of PCNS electrode. As a result, PCNS700 and PCNS900 show notably larger specific capacitance than PCNS due to their great larger surface specific areas and more structural orderings in graphitic layer stacking. However, PCNS700 shows a lager specific capacitance of 146.75 F/g than PCNS900 (132 F/g) due to its higher number of surface functional groups than PCNS900, though its lower specific surface area. The pore size distribution has a huge influence on the supercapacitor rate capability as the PCNS900 which has more mesopores and the most structural orderings in graphitic layer stacking shows excellent rate capability as well as superior long-term cycling stability (97.5% capacitance retention over 10000 cycles). In summary, PCNS obtained by hydrothermal synthesis through using block copolymer F108 as soft template shows the special physicochemical properties which make it an ideal candidate for the electrode materials of supercapacitor. Moreover, the larger the specific area, more structural orderings in graphitic layer stacking, more appropriate content of mesopores and surface functional groups, the superior performance the electrode materials of surpercapacitor exhibit.