Coatings play a crucial role in the functionality of vacuum chambers in particle accelerators, serving a dual goal by efficiently facilitating pumping and mitigating electron cloud effects. However, their impact on the surface impedance of the chamber walls raises concerns, potentially affecting the machine performance and imposing limitations on achievable energies and currents. Therefore, an electromagnetic characterization is essential for a comprehensive study of accelerator structures, particularly in the context of the next-generation machines where the demand for extremely short particle bunches accentuates the importance of evaluating material responses in the very-high-frequency region. We present a technique for probing the sub-THz response of coating materials by measuring pulsed signals passing through a specifically designed waveguide, in which is placed a slab with the deposited material under test. The proposed methodology allows for a comprehensive exploration of the electromagnetic properties of the most used technical surfaces (substrate plus coatings) in accelerators under realistic conditions, providing valuable insights into their behavior in the sub-THz frequency range. The experimental data of three different Non-Evaporable Getter coating samples, prepared on a copper substrate at the CERN deposition facilities under different sputtering conditions, are discussed. The findings contribute to a deeper understanding of the complex interactions between coatings and accelerator structures, with the aim of optimizing performance and efficiency in the evolving landscape of particle acceleration technologies. The limitations and advantages of the technique are also reported.