The feasibility of employing nanofiltration for the removal of chromium (VI) from wastewater was investigated. Poly (m-phenylene isophthalamide) (PMIA) was used to fabricate asymmetric nanofiltration membrane through the phase-inversion technique. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the obtained membrane, and the both confirmed a much smoother surface which could reduce membrane fouling. The PMIA membrane showed different rejections to electrolytes in a sequence of Na2SO4 > MgSO4 > NaCl > MgCl2, which was similar to the sequence of the negatively charged nanofiltration membranes. Separation experiments on chromium(VI) solution were conducted at various operating conditions, such as feed concentration, applied pressure and pH. It is concluded that chromium(VI) could be effectively removed from chromium-containing wastewater by the PMIA nanofiltration membranes while maintaining their pollution resistance under alkaline condition.