In polymer composites, montmorillonite nanosheets are crucial as fire retardants, reinforcers, anti-corrosives, detoxifying agents and ultraviolet-protection agents. However, the quality of montmorillonite nanosheets can be improved by optimizing the raw bentonite purification process in which undesirable phases are removed. Optimization of Iranian calcium bentonite purification for nanomontmorillonite synthesis considering various parameters based on various physical approaches to dispersion and ultrasonication was investigated; the calcium bentonite purification was performed using sodium hexametaphosphate followed by either sedimentation or centrifugation, and the nanomontmorillonite synthesis was performed using ultrasonic treatment. The effects of suspension concentration, milling type, pH and centrifugation duration and speed on the separation of various impure phases were evaluated qualitatively and optimized. The raw and purified bentonite and the synthesized nanomontmorillonite were characterized using X-ray powder diffraction, X-ray fluorescence spectroscopy, Fourier-transform infrared spectroscopy and scanning electron microscopy. The cation-exchange capacity was also measured in the raw and purified samples. Optimal experimental conditions in the dispersed samples were achieved at a 2.5 wt.% concentration of bentonite suspension and planetary milling at pH 7. While the ultrasonic treatment was more effective than the dispersion approach for cristobalite elimination, a smaller lateral size of the montmorillonite sheets, optimized at 0.5 wt.% concentration of the suspension, was achieved. The increased cation-exchange capacity after the purification improved the exfoliation and delamination of montmorillonite nanosheets in the presence of cetyltrimethylammonium bromide as the surfactant. The interplanar spacing of (001) planes of 15 Å in raw bentonite shifted to 21 Å and 19 Å in purified and non-purified samples, respectively, after synthesis.