The detection and quantification of fractures in rocks, as well as the detection of lithological changes, are of particular interest in scientific fields, such as construction materials, geotechnics, reservoirs and the diagnostics of dielectric composite materials and cultural heritage objects. Therefore, different methods and techniques have been developed and improved over the years to provide solutions, e.g., seismic, ground-penetrating radar and X-ray microtomography. However, there are always trade-offs, such as spatial resolution, investigated volume and rock penetration depth. At present, high-frequency radars (>60 GHz) are available on the market, which are compact in size and capable of imaging large areas in short periods of time. However, the few rock applications that have been carried out have not provided any information on whether these radars would be useful for detecting fractures and lithological changes in rocks. Therefore, in this work, we performed different experiments on construction and reservoir rocks using a frequency-modulated continuous wave radar working at 300 GHz to evaluate its viability in this type of application. The results showed that the radar quantified millimeter fractures at a 1 cm rock penetration depth with a sensitivity of 500 µm. Furthermore, lithological changes were identified, even when detecting interfaces generated by the artificial union of two samples from the same rock.