Integrating polyaniline (PANI) with different dimensional carbon materials is considered as a promising strategy to solve the disadvantages of PANI electrodes, such as low rate capability and poor cyclic stability. In this work, a novel layer-by-layer sandwiched graphene/PANI nanorods/carbon nanotubes (G/PANI/CNTs) heterostructure has been synthesized. The morphology of the heterostructures has been characterized by XRD, Raman spectroscopy, N2 adsorption-desorption, XPS, FESEM and TEM. The obtained new layer-by-layer sandwiched heterostructures exhibit intimate interface contacts, fully network-structured CNTs coating, dual physical supports and synergistic effects, which can effective host the electrochemical properties of PANI with the electrolyte and restrain the volumetric changes of PANI. As a result, the electrodes exhibit high specific capacitance (638 F g-1 at 0.5 A g−1), good rate capability (88.2% retention from 0.5 A g−1 to 10 A g−1) and long cycle stability (93% of the initial specific capacitance after 2000 cycles) when the amount of CNTs is 2 mg. Moreover, a possible mechanism for good performance of the layer-by-layer sandwiched heterostructures has been systematically studied. We believe that this strategy will open up an avenue for the rational design of sandwich structured electrodes for high performance supercapacitors and other electronic devices.