This work reports the application of bismuth bulk electrode (BiBE) for the determination of 2‐methyl‐4,6‐dinitrophenol (MDNP) by differential pulse voltammetry (DPV) in Britton‐Robinson buffer of pH 12.0 as an optimal medium. BiBE was prepared by transferring molten bismuth into a glass tube under constant stream of nitrogen. The linear concentration dependences were measured from 1 to 10 μmol ⋅ L−1 and from 10 to 100 μmol ⋅ L−1 by using optimum accumulation potential of −0.7 V and optimum accumulation time 30 s. Under these conditions limit of determination and limit of quantification was 0.45 and 1.5 μmol ⋅ L−1, respectively. The developed method was successfully applied for the analysis of tap water as a model sample.