A new approach, combining in-situ sol-gel process with electrospinning, was used to prepare magnetic barium acetate/manganese acetate/poly (vinyl alcohol) (PVA) composite nanofibers. The composite gel was synthesized by sol-gel method in the presence of 10 wt.% PVA aqueous solution. PVA was used as stabilizer and polymeric matrix. The resultant barium acetate/manganese acetate/PVA composite nanofibers were calcined at 1023 K for 5 h. This formed BaO/MnO nanocomposite crystalline fibers with average diameter less than 100 nm and were characterized with Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Energy Dispersive X-ray Analysis (EDAX), powder X-ray diffractometer (XRD), UV-Vis-Spectroscopy (UV) and Vibrating Sample Magnetometer (VSM) respectively. These composite fibers exhibited a uniform cylindrical morphology, with the BaO/MnO nanoparticles implanted in the fibers. M-H curves were obtained at 300 K and 20 K. From the M-H curves, room temperature ferromagnetism was observed at 300 K. At low temperatures, the ferromagnetic behavior was masked by the paramagnetic behavior. The saturation magnetization at 300 K was found to be 0.004 emu /g and the saturation magnetization at 20 K was found to be 0.658 emu /g. The magnetization at 20 K was found to be very large and it was several times larger than at 300 K. (C) 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)