Cylindrical-electrode-assisted solution blowing spinning (CSBS) is a novel nanofiber preparation method. The electric field of CSBS not only is one of the main innovations of this technology but also plays a key role in the preparation of nanofibers. In this article, the electric field of CSBS and the influences of electric field on the preparation of nanofibers were studied systematically for the first time by simulations, theoretical analyses, and experiments. This paper innovatively established the coaxial capacitor model for studying the CSBS electric field. The effects of electric field on the preparation and morphology of CSBS nanofibers were theoretically investigated by using this model. The theoretical formulas that can express the relationships between the various electric field variables were obtained. The electric field strength distribution, voltage distribution, and the relationships between the electric field parameters of CSBS were obtained by finite element simulations. The simulations’ results show that reducing the diameter of cylinder (DC) or increasing the voltage increase the electric field strength of the jet surface. Experimental results reveal that increasing voltage or reducing DC can reduce the diameter of nanofibers. The experimental and simulation results prove the correctness of the theoretical research conclusions. The theoretical and simulation conclusions of this paper lay a theoretical foundation for further study of CSBS electric field. The experimental conclusions can directly guide the controllable preparation of CSBS nanofibers.