A numerical simulation of optimization all of electrospinning processing parameters to obtain smallest nanofiber diameter have been performed by employing genetic algorithm (GA). Fitness function in genetic algorithm methods, which was different for each parameter, was determined by simulation approach based on the Reneker’s model. Moreover, others genetic algorithm parameter, namely length of population, crossover and mutation were applied to get the optimum electrospinning processing parameters. In addition, minimum fiber diameter, 32 nm, was achieved from a simulation by applied the optimum parameters of electrospinning. This finding may be useful for process control and prediction of electrospun fiber production. In this paper, it is also compared between predicted parameters with some experimental results.