Cerium nitrate/polyacrylonitrile (Ce(NO3)3/PAN) fibers were synthesized by electrospinning using PAN as template, Ce(NO3)3·6H2O as raw material. Cerium oxide (CeO2) micro-nanofibers were obtained by calcination in air. The morphology and structure of CeO2 micro-nanofibers were characterized by XRD, BET and SEM. The fluoride removal performance of CeO2 micro-nanofibers in aqueous solution was investigated by static experimental data. The influences of solution pH value, initial F- concentration and coexistent anions on the adsorption performance were studied. The results show that the adsorption capacity of CeO2 micro-nanofibers for F- is the best at pH=3, and it increases as F- concentration increases. The adsorption isotherm of F- on CeO2 micro-nanofibers fits the Langmuir model, and the second-order kinetics can well describe the adsorption process of F- on CeO2 micro-nanofibers. CeO2 micro-nanofibers have excellent fluoride removal performance, which can provide a theoretical reference for its practical application.