In this work, metallic 1T-MoS2/polyaniline (PANI) heterostructures with unique alternating arrangement are fabricated via an electrostatic attraction-induced self-assembly approach. Negatively charged metallic 1T-MoS2 monolayers are first obtained by chemical exfoliation, followed by the mixing with PANI and acidification. The neutralization of surface charges triggers spontaneous self-assembly, leading to the formation of alternating stacked 1T-MoS2/PANI heterostructures. Such unique architecture maximizes the interfacial contact between metallic 1T-MoS2 and PANI and enhances synergistic effect between them. The close atomic contact not only greatly improves the electron and ion transport of the nanocomposites, but also gives rise to good structural stability due to the strong interactions between the intimately contacted 1T-MoS2 and PANI. Furthermore, the compatibility of the nanocomposites with the aqueous electrolyte is also greatly improved. As a result, high specific capacitance and excellent cycling stability are achieved when the heterostructures are studied as electrode materials in supercapacitors. The capacitance retention is up to 91% at 10 A/g after 2000 cycles.