Molecularly imprinted polyphosphazenes are presented as sensitive coatings for the detection of rifamycin SV in water. These membranes were combined with voltammetric transduction using glassy carbon (GC) working electrodes. The receptor layers were obtained by the drop-coating technique using tetrahydrofuran (THF) solutions containing 0.27 % (m/v) of the polymer and different amounts of template (0.03–0.17 %, m/v). Evaporation of THF results on a water insoluble membrane, which shows good adherence to the GC electrode surface. After removal of the template from the solid polymer membrane, the binding of rifamycin SV was examined by equilibrating the membrane in an aqueous solution of the template. The amount of bound rifamycin SV was measured by cyclic voltammetry or differential pulse voltammetry. Similar experiments were carried out with imprinted membranes using rifampicin as template. Less effective binding was obtained for rifamycin SV in the rifampicin-imprinted polymer. The rifamycin SV sensitive electrode, constructed using the corresponding molecularly imprinted polymer, allows rifamycin SV measurement in the concentration interval between 2.5×10−7 and 6.3×10−6 M.