Poly Vinylidene Fluoride (PVDF) because of its piezoelectric properties has been applied in different applications such as smart textiles, medical application and membranes for energy harvesting. It was declared that nanofibres diameters and electrospinning parameters could be enhanced the piezoelectric properties of these materials. The main objective of this paper is applying the Genetic Algorithm (GA) to determine the optimum condition of solution parameters and processing conditions based on the desired diameter size of PVDF fibers to produce the fibers without any structural faults. In this method, The Fitness function was determined by a simple analytical model presented by Fridrikh. Toward approving the GA results the experimental tests were done. the effect of four parameters such as flow rate of the polymer solution, electrospinning voltage, electrospinning distance and polymer concentration on the fiber formation and fiber diameter size of electrospun PVDF fibers have been explored by Scanning Electron Microscopy (SEM) to attest the accuracy of the model. Assessment of experimental and theoretical results show that electrospinning parameters determined by GA method leads to achieve desire fiber diameters. Because of time and energy consuming of electrospinning process, the GA method may be useful to achieve desired fiber diameter by determining electrospinning parameters for polymers prior to fiber production.