Increasing demands forharvesting energy from other sources of energy than fossil fuel and oil haveled to an upsurge of interest in nano-structured materials such as piezoelectric nanofibers and nanowebs to harvest energy from environmental movements. Previous research introduced a suitable nanogenerator package to have higher output voltage needless of the post-treatment process. Electrospinning of PVDF (polyvinylidene fluoride) with LiCl (lithium chloride) increases the beta-crystalline phase and thus piezoelectric effect. This article presentsan FEM (finite element method) model for the electrospun PVDF/LiCl nanogenerator to determine the piezoelectric constant base on the energy approach method. An experimental and analytical procedure has been developed to determine the piezoelectric coupling coefficient and results validation. The nanogenerator package was modeled as a multilayer structure. The excitation method for the nanogenerator package was dropping a ball on the sample from different heights. The determinations of electrospun nanogenerator coupling coefficients are an important factor in the final application of these types of nanogenerators that have not beenstudied yet.