Maltodextrins (dextrose equivalent (DE) 4.0-7.0, 13.0-17.0, and 16.5-19.5) are proposed as novel chiral selectors for the construction of potentiometric, enantioselective membrane electrodes. The potentiometric, enantioselective membrane electrodes can be used reliably for the assay of S-captopril as raw material and in pharmaceutical formulations such as Novocaptopril tablets, by use of direct potentiometry. The best response was obtained when maltodextrin with higher DE was used for construction of the electrode. The best enantioselectivity and time-stability was achieved for the lower DE maltodextrin. L-proline was found to be the main interferent for all the proposed electrodes. The surface of the electrodes can be regenerated by simply polishing; this furnishes a fresh surface ready for use in a new assay.