A novel pH sensitive membrane (pHS-M) with mechanical integrity is synthesized firstly by two nozzles electrospining in this work. We report an excellent strategy here to combine indicative nanofiber from 9% PAN solution and micro-sized fibers from 20% PA-66 solution homogeneously in one electrospinning setup. The pH indicative property of electrospun sheet can be achieved by PAN nanofibers that first aminating with ethylenediamine and then immobilizing phenolphthalein covalently through a Mannich reaction, while micro-sized PA-66 fibers are responsible for the improvement of mechanical property of electrospun mat due to their elastic and flexible behavior. The composite membrane was characterized by SEM, FTIR and UV-vis spectroscopy. Results show that two kinds of pH sensitive membranes (single PAN nanofibers (pHS-NF) or composite PAN/PA-66 fiber (pHS-CF)) all exhibited remarkable color change from pale yellow to violet in a wide range of alkaline solution and rapid response time within 100 s. But after added of microfiber, the tensile strength was enhanced from 1.3 MPa to 6.90 MPa prominently which is beneficial to put the membrane into practice. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.