Rotating compensator multichannel spectroscopic ellipsometry has been employed to determine the optical functions of various liquids used in chemistry. We attempted three different measurement configurations: (1) air-liquid interface, (2) prism-liquid interface, and (3) liquid-sample interface. In prism-liquid interface, we found that the prism surface had roughness and it should be considered in analysis for accurate results. In liquidsample interface, we had much higher reflection, better sensitivity, and less limitation compared to the other two configurations when crystalline silicon was used as reference sample. We discuss the merit of each configuration and present the optical functions of various liquids. Also we demonstrate Bruggeman effective medium theory to determine the optical properties of mixed liquid.