The interaction between multiwalled carbon nanotubes (MWCNTs) and aqueous poly(diallyl dimethylammonium) chloride (PDDA) was studied by X-ray photoelectron (XPS) and photoacoustic Fourier transform infrared (PA-FTIR) spectroscopies. We have found that the mild sonication of MWCNTs in aqueous PDDA results in a significant improvement of CNT dispersibility and greatly enhances their adhesion to Au and Si substrates. The MWCNT−PDDA interaction is due to the presence of an unsaturated contaminant in the PDDA chain, as confirmed by both XPS and PA-FTIR, which enters into a π−π interaction with the CNTs. Electrostatic group repulsions of the coated CNTs then provide the dispersibility and adhesion.