It is challenging to effectively purge wastewater containing heavy metal ions at low concentration. In order to remove trace Cr (VI) from wastewater efficiently, a positively charged microporous membrane was prepared by firstly non-solvent induced phase separation (NIPS) of amphiphilic polymer and secondly surface quaternization modification. The morphologies, surface roughness, surface charge, hydrophilicity, and pore size of membranes were characterized. Based on the dual action of micellar adsorption and charge repulsion, when surfactant is 4 mM and Cr (VI) is 60 ppm, the surface quaternization membrane (Q-MPVD) achieves 99.8 % Cr (VI) rejection simultaneously accompanied by a permeability of 100 LMH/bar. Meanwhile, the effects of STAC concentration, Cr (VI) concentration, pH as well as inorganic salt concentration on the composite micellar size, and Cr (VI) rejection performance were investigated, respectively. Moreover, the Q-MPVD membrane shows an excellent separation stability over a wide pH range, indicating its application perspective in engineering process. In summary, this work provided a positively charged membrane with high-efficiency performance for treating practical trace Cr (VI)-containing industrial wastewater.