This paper describes a new distance transform method used for measuring fiber diameter in electrospun nanofiber webs. In this algorithm, the effect of intersection is eliminated, which brings more accuracy to the measurement. The method is tested by a series of simulated images with known characteristics as well as some real webs obtained from electrospinning of PVA. Our method is compared with the distance transform method. The results obtained by our method were significantly better than the distance transform, indicating that the new method could successfully be used to measure electrospun fiber diameter.