Due to the advantages of large interstitial sites, antisolubility, and reversible insertion and extraction of anions, polypyrrole (PPy) has become an excellent P-type electrode material for dual-ion batteries. Unfortunately, PPy electrodes inevitably suffer from low specific capacity and poor cycle stability because of structural disintegration during repeated cycling as well as poor doping ability brought on by aggregation or cross-linking within the PPy chain. In this work, PPy with different proportions of coupling mode (α-α, α-β, or β-β coupling) was derived from different preparation methods. Among them, PPy derived from the interfacial frozen polymerization method (I-PPy) is dominated by the α-α coupling mode and possesses the best anion doping ability and the highest specific capacity of 119 mAh g