A novel nanosilver/dodecane modified electrode was fabricated and employed for electrochemical sensing of fenitrothion presented in the environmental samples such as potatoes and paddy. The electrocatalytic activity of the modified electrode exhibited a lower reduction potential and higher sensing current in the detection of fenitrothion. A least value of limit of detection (LOD) was observed compared to that of the electrodes employed. The electrode was found to be exceptionally stable and have constant sensitivity for many cycles of analysis. The result observed in the electrochemical approach was well comparable with that by HPLC technique. The modified electrode is certainly a viable and an alternative to the high cost HPLC technique in detecting fenitrothion kind of pesticide samples.