Quick and robust analytical methods are of vital necessity in medicine and biology, making the synthesis of the electroactive substrates for the sensing of medically relevant chemicals a promising area of material science. Rare earth cuprates, mostly famous for high-temperature superconductivity, continue to exhibit encouraging electroactivity toward surface selective oxidation of biologically active compounds. Samarium cuprate reported in this paper showed developed surface with unique porous morphology and good conductivity – a set of prerequisites for sensing material. Further studies confirmed excellent samarium cuprate-based carbon paste electrode sensitivity of enalapril maleate and helped to develop an analytical method with selectivity and stability applicable for wider use.