In order to meet the demand for miniaturized devices, ferroelectric ceramics with micro- or nano-crystal particle size are among the primary needs. In this work, we fabricated 5 mol.% cerium-doped BaTiO3 (CBTO) nanofibers by using sol-gel combined with electrospinning. The mechanism of doping has been investigated in detail by multiple methods. In addition, the dielectric and ferroelectric properties of the obtained CBTO ceramics fabricated by these nanofibers were investigated. Their phase transition temperature shifted to a lower temperature due to the cerium dopant and size effects. An obvious decrease of ferroelectricity of the ceramics was observed, possibly due to the existence of polar nano-regions and cerium ions. The lower curie temperature of CBTO ceramics makes it possible for over-temperature protection applications.