In this work, GC electrodes modified with thick electrospun nanofibrous Nafion webs were characterized using scanning electron microscopy (SEM) and cyclic voltammetry (CV) and used for the extraction and electrochemical detection of cadmium by differential pulse voltammetry. Cadmium was detected after 10 min incubation at open circuit followed by anodic stripping using 60 s reduction at -1.4 V. The electrode yielded well-defined, undistorted and reproducible (RSD of 7.0?% based on 10 measurements) voltammetric response with two linear ranges from 0.1 to 3 mu M (R2=0.994 ) and from 3 to 10 mu M (R2=0.977) and a detection limit and sensitivity of 0.01 mu M and 32 and 7.725 mu A/mu M for both linear portions of the curve respectively.