Branch-like carboxylated MWCNTs (f-MWCNTs)/Chitosan (CS) nanofibrous membranes were developed based on the simultaneous electrospinning of CS fibers and spraying (high-pressure-assisted spraying or electrospraying) of f-MWCNTs nanoparticles, thus highlighting new avenues to the development of composite membranes with multilevel structures and added functionalities. Compared with pristine CS and blending f-MWCNTs/CS nanofibrous membranes which was directly electrospun from f-MWCNTs/CS blends, the as-prepared branch-like nanofibrous membranes at the thickness of only 30 mu m displayed significantly improved rejection (improved about 161-166% and 80-90%, respectively) toward both methylene blue and methyl orange, yet attaining high water flux (3543.50 and 3757.36 L/m(2) h, respectively) at a low pressure of 0.2 bar. Therefore, the simultaneous electrospinning and spraying process has opened up an innovative alternative for the fabrication of structured membranes rather than using blending process in wastewater treatment. (C) 2015 Elsevier B.V. All rights reserved.