Composites of polyaniline/carbon microcoils (PANI/CMCs) were prepared by microemulsion-polymerization method. The observation by scanning electron microscopy (SEM) showed that the surface of the CMCs became rough due to the coverage of PANI on the surface after the synthesis process. The infrared spectroscopy measurement proved the presence of chemical bonding between PANI and CMCs. When the volume ratio of chloroform, as co-emulsifier, to the total reaction matters was 1: 24, the maximum amount of PANI coverage can be acquired, which well grafted on the surface of CMCs. Results of constant current charge-discharge and cyclic voltammetry tests show that in comparison with the single PANI or CMCs, the composites possess superior capacitive performance with a specific capacitance 134.8 F·g^-1 and an excellent cycling stability with a remaining capacitance 63.3% after 750 cycles.