The development of a novel, molecularly imprinted polymer (MIP), based on polyaniline nanofibers (PANInfs) for the electrochemical detection of aldicarb (Ald), is reported. PANInfs are synthesized by the simple interfacial polymerization method with and without the presence of Ald. A part of the PANInfs containing Ald (MIP‐Ald) is dispersed in deionized (DI) water and sonicated to remove Ald and obtain MIP. The MIP, bare PANInfs (non‐imprinted polymer or [NIP]), and the nonsonicated polymer (MIP‐Ald) are separately drop cast onto hydrolyzed indium tin oxide (ITO)‐coated glass. All these three types of electrodes are characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and cyclic voltammetry (CV) techniques to understand their structure, morphology, and successful synthesis of the desired compounds. The electrochemical detection of Ald is conducted using differential pulse voltammetry (DPV). This MIP‐based sensor is able to detect Ald in the range of 50–80 nM with a limit of detection 500 pM L−1, having a sensitivity of 6.83 ± 0.09 μA nM−1 cm−2, making it an ideal candidate for Ald detection. This method is adapted to synthesize MIPs of other pesticides by which the cost and the detection time is reduced considerably.