The pore size and its distribution are the two main geometrical properties of nanofibrous membranes in various applications such as filtration and tissue engineering. In the current paper, a modified approach (model) is suggested to predict pore size and its distribution in nanofibrous membranes. In the present work, inter-fibre pores are considered as polygons arising from the fibre contacts. For the first time, these polygons are assumed to be three-, four-and five-gons, and the hydraulic radius of the pores was obtained instead of the equal radius. The pore size of multilayer mats was provided with a different insight. The pore mean size and its distribution were obtained by statistical methods. In order to validate the model, polycaprolactone (PCL) nanofibrous mats were electrospun, and the mean pore size and its distribution were measured using porosimetry. It was found that the probability distribution function of the pore size in both single and multi nanofibrous layers was the Gamma function with two parameters. The effect of the fibre width and porosity raise was increasing of mean pore diameter of multilayer networks. A comparison between the modified model and previous models revealed that the modified approach was more realistic.