Carbon nanofibers embedded with ultrafine zirconia nanoparticles (ZrO2-CNFs) are fabricated via a new methodology. Polyvinylpyrrolidone (PVP) and polymethylmethacrylate (PMMA) binary polymers containing zirconium n-butoxide are first dissolved in dimethylformamide, and the resulting solution is electrospun and heat-treated. The tetragonal zirconia nanoparticles formed, with a size of 5 +/- 2 nm in diameter, are uniformly distributed in the carbon nanofibres. Using Nafion as an additive, ZrO2-CNFs are drop-cast onto the glassy carbon electrode (ZrO2-CNF/GCE) and the modified electrode is then applied to detect methyl parathion (MP) using differential pulse voltammetry. Two linear relationships are found at the concentration ranges of 1 x 10(-9) -2 x 10(-8) g/L and 2 x10(-8) -2 x 10(-7) g/L, with a detection limit of 3.4x10(-10) g/L (S/N>3). The electrospun-based ZrO2-CNF is a very promising coating material for electrochemical sensing of organophosphorus compounds.