A solution for electro-spinning of fibers was prepared via non-hydrolytic sol-gel method with ethanol and dimethyl formamide (DMF) as solvent, MgCl₂ and AlCl₃ as raw material and polyvinylpyrrolidone (PVP) as additive. With the above solution, precursor fibers of magnesia-alumina spinel were prepared by electrospinning technology, which then were calcined at 900℃ to finally produce fibers of magnesia-alumina spinel. The effect of gelation temperature, the content of gel and PVP on the phase composition and microstructure of magnesia-alumina spinel fibers was studied by XRD, FTIR, SEM and TEM. The result shows that magnesia-alumina spinel fibers could be produced with the fiber precursor prepared with the fresh solution which was not subjected to sol-gel treatment, but such fibers were cross-linked seriously and on which there existed significant amount of moniliform particles; For those made of the fiber precursor prepared with the solution after gelation at 120℃, such fibers were apt to fracture and the diameter of which increased with the increasing dosage of gel and PVP; For those made of the fiber precursor prepared with the solution after gelation at 100℃ with a dosage of 0.068 mol/L gel and 0.045 g/mL PVP, the fibers were smooth, continuous and homogeneous with an average diameter 121 nm, and furthermore, these fibers still showed good a morphology even after calcined at 1600℃.