Multi-wall carbon nanotubes (MWCNTs) decorated with Fe3O4 nanoparticles (MWCNTs/Fe3O4) were modified by polyaniline (PANI). The adsorption kinetics of methyl orange (MO) on MWCNTs/Fe3O4/PANI could be fitted well by the pseudo-second-order model. The adsorption of MO on MWCNTs/Fe3O4/PANI was strongly dependent on pH values. The Langmuir isotherm model fitted MO adsorption isotherm better than the Freundlich model. The hierarchical MWCNTs/Fe3O4/PANI showed high adsorption capacity toward ionic dyes (446.25mgg−1 for MO and 417.38mgg−1 for Congo red (CR)). The nitrogen-containing functional groups of PANI decorated on MWCNTs/Fe3O4/PANI contributed to many effective adsorption sites and thus increased the adsorption capacity toward MO and CR. Moreover, PANI prevented Fe3O4 nanoparticles from dissolution, and hence improved the stability of MWCNTs/Fe3O4/PANI in solution. The experimental results showed that the MWCNTs/Fe3O4/PANI composite was a promising magnetic material for the preconcentration and separation of ionic dye pollutants from aqueous solutions in environmental pollution cleanup.