Multiferroic CoFe2O4–Ba0.95Ca0.05Ti0.89Sn0.11O3 composite nanofibers (CFO–BCTSn NFs) were synthesized using a sol–gel electrospinning method. Scanning electron microscopy revealed the morphology of the composites, with fiber diameters ranging from 120 to 150 nm. Transmission electron microscopy confirmed the structure of the nanofibers, while X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy verified the formation of the spinel structure of CFO and the perovskite structure of BCTSn, with no additional phases detected. The magnetic properties of the CFO–BCTSn NFs were demonstrated by magnetic hysteresis loops (M-H), and piezoresponse force microscopy confirmed their piezoelectricity. Magnetoelectric coupling was evidenced by comparing the M-H hysteresis loops of electrically poled and unpoled CFO–BCTSn NFs samples. These composite nanofibers have the potential to be utilized in innovative, lead-free magnetoelectric and magnetic field sensing technologies at the nanoscale.