In this study, new adsorbents were prepared by modifying a montmorillonite clay (Mt) with cethyltrimethyl ammonium bromide (CTAB) to form CTAB-Mt, followed by a second modification process with polyaniline (PAni) to form PAni@CTAB-Mt by in situ polymerization of aniline. X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), cyclic voltammetry (CV) and the Brunauer–Emmett–Teller (BET) technique were used to characterize the samples. These adsorbents were used in a batch process to remove methylene blue (MB) from aqueous solution. Factors investigated included initial pH of the solution, contact time and temperature. The adsorption data fit the Freundlich isotherm better than the Langmuir and Temkin isotherms. The maximum adsorption capacities (qeq) obtained were 108.82 mg·g−1, 71.20 mg·g−1 and 57.36 mg·g−1 for PAni@CTAB-Mt, CTAB-Mt and Mt, respectively. The enhanced adsorption capability of the hybrid material is due to increase in surface area and pore volume of the PAni@CTAB-Mt adsorbent. The adsorption results were found to fit well with the pseudo-second-order kinetics model, with highest correlation coefficient (R2) values of 0.954, 0.942 and 0.958 for Mt, CTAB-Mt and PAni@CTAB-Mt adsorbents, respectively. The pH and temperature had a significant effect on the adsorption process, and the negative values of ΔG suggest that the adsorption process was spontaneous and feasible. The desorption and reusability experiment indicated that PAni@CTAB-Mt has the potential to be a reusable adsorbent for MB removal.