Electrospun nanofibers with designed or controlled structures have drawn much attention. In this study, we report an interesting new closed-loop structure in individual cerium nitrate/polyvinyl alcohol (Ce(NO3)3/PVA) and NaCl/PVA fibers, which are fabricated by electrospinning with a nail collector. The electrospinning parameters such as voltage and Ce(NO3)3 (or NaCl) concentration are examined for the formation of the closed-loop structure. The results suggest that the increase of the spinning voltage or addition of Ce(NO3)3 (or NaCl) is favorable for the formation of the closed-loop structure, and the increase of loop numbers and the decrease of loop size. Further analyses indicate that the formation mechanism of the closed-loop fibers can be predominantly attributed to the Coulomb repulsion in the charged jets.