The δ-MnO2 exhibits an ideal capacitive deionization (CDI) electrode for the efficient removal of ammonium ions (NH4+), owing to its unique layered structure that facilitates effective insertion and extraction of ions. However, MnO2 is constrained by self-aggregation, inadequate electrical conductivity, and sluggish reaction kinetics in practical applications, leading to subpar ammonium removal performance. Here, the polyaniline (PANI) intercalated MnO2 and carbon nanotubes (CNTs) composites (P/M-C-X) were synthesized by a straightforward and swift one-step inorganic/organic interface reaction using the chemical traction effect of aniline. The synergistic effect of the increased layer spacing and the introduced oxygen vacancy after PANI intercalated and the 1D/2D conductive interconnect structure constructed by CNTs can effectively improve the electrical conductivity, promote ions/electrons diffusion, and enhance the charge reaction kinetics. As results, P/M-C-50 exhibits excellent NH4+ removal performance, including the maximum salt adsorption capacity (SAC) (160.0 mg g−1), ultra-high salt adsorption rate (SAR) (1.07 mg g−1 s−1), and good cyclic stability. Furthermore, the comprehension of NH4+ storage mechanism has been enhanced through structural characterization, electrochemical analysis, and theoretical calculation. This study shows that P/M-C-50 has broad potential as a CDI ammonium removal electrode, and lays a solid foundation for the effective recovery and reuse of ammonium resources.