Fiber diameter is the most important characteristic in electrospun nonwoven webs. Understanding how it is influenced by the electrospinning parameters is essential to produce webs with desired characteristics. In this contribution, Direct Tracking method for measuring electrospun fiber diameter is described. To evaluate the accuracy of the technique, a simulation algorithm for generating webs with known characteristics was employed. To verify the applicability of the method on real samples, an electrospun polyvinyl alcohol (PVA) mat, as a representative of real webs, was used. Since the Direct Tracking method uses a binary image as its input, local thresholding was applied to segment the SEM micrograph of the electrospun web. The results indicate that the method could be used successfully for determining fiber diameter in electrospun nonwoven webs.