An optical scheme based on Stokes–Mueller formalism and rotating-wave-plate Stokes polarimeter is successfully developed to measure the optical rotation angle in a chiral medium. The average relative error in the measured rotation angle of a half-wave plate is determined to be 1.16%. The average relative error in the measured rotation angles of glucose solutions with concentrations ranging from 0 to 1.2g/dl is determined to be 3.78%. The correlation coefficient between the measured rotation angle and the glucose concentration is found to be 0.99950, while the standard deviation is just 0.00376°. From the inspection of measured rotation angle in the sol–gel materials containing C 17 H 17 ClO 6 with concentrations ranging from 0 to 0.0665g/ml, the average relative error in the measured rotation angles is determined to be 3.63%. Consequently, the derived algorithm for measuring the rotation angle of a chiral medium is feasible, and the developed system is evaluated with a precision of 5.4% approximately in rotation angle measurement.