Nanostructures of polypyrrole with controlled uniform morphologies have been synthesized using assembled surfactant aggregates as templates. The effects of hydrophobic chain length of surfactant on particle size and electrochemical performance of polypyrrole nanospheres are systematically studied. The particle size and morphology of the nanospheres are observed by scanning electron microscope and transmission electron microscope, and at the same time, the nitrogen adsorption and desorption test of polypyrrole spheres are carried out. The results show that changing the length of hydrophobic chain of surfactant is not only an effective control of particle size and morphology, but also a significant improvement on the pore structure. With the increase in alkyl chain length, the particle size decreases, and the specific surface area and pore volume increase. The polypyrrole nanosphere prepared by long hydrophobic chain surfactant shows small impedance and high electrochemical capacity about 232 F g(-1) at 1.0 A g(-1), and the results suggest that we can fabricate high specific surface area polypyrrole nanosphere which has excellent electrochemical performance by the regulation of hydrophobic chain length. Our work provides a novel synthetic strategy for the fabrication of nanospheres for the construction of high-performance supercapacitors by optimizing the hydrophobic chain length.