Complex permittivity of a number of liquids and binary mixtures has been studied by measurement using the waveguide techniques at the X and Ku band. Particular pieces of WR90 and WR62 waveguides were designed for the measurement of liquid materials. The custom designed TRL calibration kits are applied for calibration of the waveguide system. The measured results of complex permittivity of liquid dielectrics, such as methanol, propyl alcohol, ethyl alcohol, chlorobenzene, dioxane, cyclohexane and binary mixtures, are presented. Particular pieces of open-ended waveguides for the X and Ku bands were also designed for holding liquids and the measured data using the open-ended waveguide technique were compared with those measured using the waveguide technique. Some of the measured results are also compared with calculated data using the Debye equation and published data measured by the Fourier transform spectroscopy.