Perovskite-type oxide LaNiO3 nanofibers (LNFs) have been successfully synthesized by electrospinning and sequential calcinations. The electrospun LNFs modified carbon paste electrode was used to construct a nonenzymatic hydrogen peroxide (H2O2) sensor and glucose biosensor for the first time. The LNFs composition was verified by X-ray diffraction, and the morphologies were examined by scanning electron microscopy and transmission electron microscopy. Cyclic voltammetry and amperometry were used to evaluate the catalytic activity of the LNFs modified electrode towards H2O2 and glucose. By using LNFs as electrocatalysts, the modified electrode showed high electrocatalytic activity for the oxidation of H2O2 and glucose. Under the optimized conditions, the H2O2 sensor exhibited a low detection limit down to 33.9 nM with a wide linear range from 0.05 to 1000 mu M. The nonenzymatic sensor also showed fast response, long-term stability as well as a low detection limit for glucose.