Poly(3,4‐ethylenedioxythiophene) films doped with Taurine ligands (PEDOT‐Tau films) were deposited from aqueous solution and made sensitive towards Mg2+ or Ca2+ ions by conditioning in a mixture of 0.5 M Taurine with saturated magnesium or calcium hydroxide. Potentiometric responses towards selected cations as well as potential transient responses were described. The elemental analysis, morphology and topography were studied to elucidate potentiometric behavior of PEDOT‐Tau films. The elemental analysis was made for freshly deposited and sensitized for magnesium and calcium films by using X‐ray Photoelectron Spectroscopy (XPS), Energy Dispersive Analysis of X‐ray (EDAX) and Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA‐ICP‐MS). The morphology and topography of such films were inspected by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM).