Electrospun materials, due to their unique properties, have found many applications in the biomedical field. Exploiting their porous nanofibrous structure, they are often used as scaffolds in tissue engineering which closely resemble a native cellular environment. The structural and mechanical properties of the substrates need to be carefully optimised to mimic cues used by the extracellular matrix to guide cells’ behaviour and improve existing scaffolds. Optimisation of these parameters is enabled by using the finite element model of electrospun structures proposed in this study. First, a fully parametric three-dimensional microscopic model of electrospun material with a random fibrous network was developed. Experimental results were obtained by testing electrospun poly(ethylene) oxide materials. Parameters of single fibres were determined by atomic force microscopy nanoindentations and used as input data for the model. The validation was performed by comparing model output data with tensile test results obtained for electrospun mats. We performed extensive analysis of model parameters correlations to understand the crucial factors and enable extrapolation of a simplified model. We found good agreement between the simulation and the experimental data. The proposed model is a potent tool in the optimisation of electrospun structures and scaffolds for enhanced regenerative therapies.