In this paper, we present our results for the anisotropic refractive index measurements of commonly used liquid crystal LC materials E7 and 5CB in the whole visible–near infrared range. In order to achieve a high accuracy in the obtained values, we have employed a combination of two techniques, namely, Mueller matrix spectroscopic ellipsometry in transmission and half-leaky-guided-mode HLGM. Measurements with the HLGM technique are usually performed at a single wavelength. In order to obtain a spectroscopic measurement based on the HLGM technique in a wide wavelength range, we modified our commercial VASE® ellipsometer. In particular, we designed a sample holder by means of which measurements in guiding structures are also possible. Thus,...