An analytical model describing the conductivity of ZnO nanofibers depending on the grains size is proposed. The research is based on the thermal dc electrical measurements of a single electrospun ZnO nanofiber calcined at different temperatures. In the our previous research, we showed that electrical conduction of ZnO nanofibers is mainly thermally activated. The activation energy of conductivity was strongly dependent on the grain size, which in turn depended on the calcination temperature. This could be due to migration of a point defect in the grain of ZnO and could change the carrier concentration. Our recent studies have shown that ZnO nanofibers behavior is consistent with the Meyer-Neldel rule. This indicates an exponential energy distribution of deep level traps in the material. Based on the theoretical assumptions and experimental data, the improved model of conductivity in a single ZnO nanofiber calcined at different temperatures was proposed.