Mg0.6Ni0.4O hollow nanofibers with diameter of 300-600 nm were successfully prepared by elecrospinning a precursor mixture of polyacrylonitrile (PAN)/(magnesium nitratenickel + nitrate), followed by calcination treatment of the electrospun polymer/inorganic composite fibers. The resulting Mg0.6Ni0.4O hollow nanofibers were characterized with X-ray diffraction, Brunauere-Emmette-Teller, FT-IR spectra and scanning electron microscopy. Mg0.6Ni0.4O hollow nanofibres were obtained after being calcined at 500.C and their surface became coarse with increasing of calcination temperatures. Possible formation mechanism for Mg0.6Ni0.4O hollow nanofibers was preliminarily proposed.