We perform measurements in the wide frequency range thanks to a unique set consisted of four-port PNA-X Vector Network Analyzers from Agilent Technologies and six pairs of Frequency Extenders for measurements up to 500 GHz. Each pair of Frequency Extenders is designed for single band of standard rectangular waveguide and allows to measure full two-port scattering matrix (amplitude and phase) with a very high dynamic range (above 100 dB). The wide frequency range and large number of measurement points (up to 32001 points) enables further processing of the measured data in the time domain. This set is used for measurements of antenna parameters, and is a part of the quasi-optical setup for the characterization of materials in the millimeter-wave and sub-terahertz ranges.