A novel membrane electrode for Pb(II) ion detection based on semi-conducting poly(m-phenylenediamine) microparticles as a unique solid ionophore was fabricated. The electrode exhibited significantly enhanced response towards Pb(II) over the concentration range from 3.16×10−6 to 0.0316M at pH 3.0–5.0 with a low detection limit of 6.31×10−7M, a high sensitivity displaying a near-Nernstian slope of 29.8mVdecade−1 for Pb(II). The electrode showed a long lifetime of 5 months and a short response time of 14s. A systematical investigation on the effect of anion excluder and various foreign ions on the selectivity of the electrode by a fixed interference method suggests that all other metal ions hardly ever interfere with the determination of Pb(II) except high concentration Hg(II). The electrode was successfully used as an indicator electrode in the potentiometric titration of Pb(II) with EDTA. Furthermore, the electrode has been used to satisfactorily analyze four types of real-world samples like spiked human urine, spiked tap water, and river water containing interfering ions like Na(I), Ca(II), Mg(II), Zn(II), Pd(II), Fe(III), K(I), Cu(II) and Hg(II) up to 8.04×10−4M, demonstrating fast response, high selectivity, good recovery (96.6–121.4%), good repeatability (RSD 0.31–6.45%), and small relative error (5.0%).