Rapid ‘in-field’ detection of environmentally hazardous organophosphorus and nitro-containing pesticides is highly essential due to the lethal effects caused by the inhibition of the activity of acetylcholinesterase (AChE). In our present study, we demonstrate a novel sensing approach for the simultaneous analysis of five widely used pesticides (methyl parathion, pendimethalin, dicloran, trifluralin, and PCNB) based on the Meisenheimer complex formation between polynitro aromatic compounds (pesticides) and a nucleophile. This colorimetric determination of pesticides involves the use of an ionic liquid, tetrabutylammonium hydroxide (TBAOH), as the nucleophile, which is titrated against different concentrations of pesticides. The addition of TBAOH to the solutions of pesticides results in the formation of intensely colored complexes, which are visualized using UV-vis and NMR spectroscopies allowing the identification of new bands and peaks corresponding to the formation of Meisenheimer complexes. The limit of detection (LOD) for targeted pesticides was found to be in the range of 0.67–10 μM. Furthermore, the practical application of this method is demonstrated by developing different paper-based sensors. Therefore, the strategy proposed here not only serves as a valuable tool that allows unskilled people to detect hazardous pesticides in agricultural products ‘on-site’ but also offers a fast and convenient protocol for the identification of dangerous nitro-containing polyaromatic groups like nitro explosives.