Average number of fiber-to-fiber contacts in a fibrous structure is a prerequisite to investigate the mechanical, optical and transport properties of stochastic nano-microfibrous networks. In this research work, based on theoretical analysis presented for the estimation of the number of contacts between fibers in electrospun random multilayer nanofibrous assembles, experimental verification for theoretical dependence of fiber diameter and network porosity on the fiber to fiber contacts has been provided. The analytical model formulated is compared with the existing theories to predict the average number of fiber contacts of nanofiber structures. The effect of fiber diameters and network porosities on average number of fiber contacts of nano-microfiber mats has been investigated. A comparison is also made between the experimental and theoretical number of inter-fiber contacts of multilayer electrospun random nano-microfibrous networks. It has been found that both the fiber diameter and the network porosity have significant effects on the properties of fiber-to-fiber contacts.