We report on a plasticized polyurethane ionophore-based thin film material (of hundreds of nanometer thickness) for simultaneous voltammetric multianalyte ion activity detection triggered by the oxidation/reduction of an underlying poly(3-octylthiophene) film. This material provides excellent mechanical, physical, and chemical robustness compared to other polymers. Polyurethane films did not exhibit leaching of lipophilic additives after rinsing with a direct water jet and exhibited resistance to detachment from the underlying electrode surface, resulting in a voltammetric current response with less than <1.5% RSD variation (n = 50). In contrast, plasticized poly(vinyl chloride), polystyrene, and poly(acrylate) ionophore-based membranes of the same thickness and composition exhibited a significant deterioration of the signal after identical treatment. While previously reported works emphasized fundamental advancement of multi-ion detection with multi-ionophore-based thin films, polyurethane thin membranes allow one to achieve real world measurements without sacrificing analytical performance. Indeed, polyurethane membranes are demonstrated to be useful for the simultaneous determination of potassium and lithium in undiluted human serum and blood with attractive precision.