The authors describe a graphite immobilized bismuth film electrode with enhanced sensitivity for the organophosphorus pesticide paraoxon. The film was formed by ex-situ electroplating of bismuth onto the large surface of a glassy carbon electrode modified with graphite nanopowder (Bi/Gr/GCE). The modified GCE was characterized by chronoamperometry using p-nitrophenol as a model nitro compound. The modification of the GCE results in an increase of the electroactive area (to 27.7 mm2) and of the electrocatalytic activity (the catalytic rate constant being 4140 L·mol−1·s−1). This results in an enhancement of the current for the electroreduction of paraoxon by a factor of 4.3 (compared to a plain GCE). The modified GCE was applied to the sensitive determination of paraoxon by differential pulse voltammetry. At a typical working potential of −0.45 V vs. Ag/AgCl, the LOD is 2 nmol·L−1 of paraoxon, which is comparable to the LOD of some cholinesterases-based electrochemical sensors and is lower than the LOD of the organophosphorus hydrolase-based electrochemical sensors for paraoxon. In addition, the new GCE is more stable than enzyme-based sensors, and it can be renewed.