The rhodamine B-attapulgite/polypyrrole (RhB-ATP/PPy) composites have been prepared by the in situ chemical oxidative polymerization method based on the self-assembly of pyrrole on the surface of the rhodamine B modified ATP (RhB-ATP). The morphologies of the RhB-ATP/PPy composites prepared with different feeding ratio of pyrrole and the RhB-ATP were compared with transmission electron microscope (TEM) technique. The electrochemical behaviors of the RhB-ATP/PPy composites were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge. The results indicated that RhB did effectively improve the electrochemical performance and cycling stability of the RhB-ATP/PPy composite electrode, although RhB showed no obvious effect on the morphology of the nanocomposites. It was attributed to the fact that RhB and ATP provided a more convenient pathway to the charge carrier and RhB made the combination of the ATP and PPy much stronger. The maximum discharge capacity of the composites electrode achieved 587Fg−1 and kept 76% of its original speciﬁc capacitance after 500 cycles.