A reflectometer calibration technique is provided that may include the use of two calibration samples in the calibration process. Further, the technique allows for calibration even in the presence of variations between the actual and assumed properties of at least one or more of the calibration samples. In addition, the technique utilizes a ratio of the measurements from the first and second calibration samples to determine the actual properties of at least one of the calibration samples. The ratio may be a ratio of the intensity reflected from the first and second calibration samples. The samples may exhibit relatively different reflective properties at the desired wavelengths. In such a technique the reflectance data of each sample may then be considered relatively decoupled from the other and actual properties of one or more of the calibration samples may be calculated. The determined actual properties may then be utilized to assist calibration of the reflectometer.