ZnO nanofibers (ZnO NFs) were fabricated by electrospinning a dimethylformamide solution of zinc acetate containing polyvinylpyrrolidone and polymethylmethacrylate binary polymer matrix, followed by calcination. The obtained ZnO NFs are composed of close-packed ZnO nanoparticles of ca.20 nm in diameter. With Nafion acting as adhesive, the ZnO NF coated glassy carbon electrode (ZnO NF/GCE) has been prepared and applied as a new sensing platform for heavy metal determination with square wave stripping voltammetry. The high surface area and the strong affinity to cadmium (Cd) render the ZnO NF/GCE sensitive to Cd ion measurement. The experiment parameters were optimized by the design of orthogonal experiment. Under the optimal conditions, the current response exhibits a good linear relationship with the concentration of Cd(II) ranging from 4.8 x 10(-9) to 1.3 x 10(-6) mol L-1,with the detection limit of 1.8 x 10(-9) mol L-1 (S/N >3). The developed sensor has been successfully applied for the determination of Cd(II) in water sample. The simultaneous analysis of Cd(II), Pb(II), Cu(II) and Hg(II) has been demonstrated to be feasible. (C) 2016 Elsevier B.V. All rights reserved.