Inulins are proposed as new electroactive materials in the design of enantioselective sensors, for the enantioanalysis of chiral drugs. Captopril was used as model analyte. Diamond and carbon paste were used as matrices for the design of the electrochemical sensors. Using differential pulse voltammetry, the linear concentration range obtained for the assay of captopril was 10(-10) - 10(-5) mol/L with detection limits up to 6.58 x 10(-12) mol/L. The recovery of S-captopril in its pharmaceutical formulation was higher than 90.00%. The main advantages of using such sensors in enantioanalysis are minimal processing of sample (usually its dissolution in water), high reliability of the analytical information, low limit of detection, and low cost of analysis. (C) 2013 The Electrochemical Society. All rights reserved.