Poly(aniline-co-o-anisidine) (P(An-co-o-As)) ionomers and poly(sodium 4-styrenesulfonate) (PSS) were layer-by-layer (LbL) assembled on carboxylic acid-functionalized multiwalled carbon nanotubes (MWNTs). The multilayered polyelectrolyte greatly enhanced the dispersibility and stability of MWNTs in aqueous solutions. More importantly, the nanocomposites showed 3 orders of magnitude of conductivity increase, 4.2 S/cm, compared to that of neat ionomers, 0.004 S/cm. The deposition procedure was monitored with zeta (zeta) potential changes. Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis), and Raman spectra confirmed charge transfer from the quinoid units of the P(An-co-o-As) to MWNTs, which effectively delocalize the electrons. Further, we explored the pH response of the assembled P(An-co-o-As)/PSS/MWNTs multilayer nanocomposites. The sharp transition of the conductivity in the pH range of 2 to 6 makes the nanocomposites promising candidates for chemical-biological sensing.