In open pit mining areas, knowledge of geotechnical conditions (e.g., overburden thickness, background slope, and fault locations) ensures geotechnical safety during exploitation as well as reclamation planning. The Greek Public Power Corporation initiated a research program after stability issues emerged on the southern side of the Mavropigi open pit mine in NW Macedonia. Geotechnical wells revealed steeply dipping bedrock and thin tectonic contact, indicating the need for the detailed imaging of the subsurface for future stability measures. For this purpose, a geophysical investigation aimed to extract information mostly for the dip of the interface between schist bedrock and overlaying Neogene sediments and/or limestones. Based on the high contrast of electrical properties between schists and limestones, as well as the differences in acoustic impedance and formation thickness, the seismic reflection and electrical resistivity tomography (ERT) methods were selected. The suitability of the seismic reflection for its application in this area was checked by generating synthetic seismic data, which resulted from the simulation of seismic wave propagation for geological models of the area. The acquisition parameters were determined after the noise test. Field seismic data processing produced a depth-migrated section, which revealed the existence of a fault. The use of dipole–dipole and gradient arrays, in 2D and 3D electrical resistivity measurements, ensured both the lateral and vertical mapping of schist bedrock and detected limestone bodies within the overburden. Also, the tectonic contact zone between limestone and schist formations was properly imaged. The comparison between geoelectrical and seismic sections indicated that the seismic reflection method provided a more accurate estimate of fault inclination. Finally, the geophysical survey enriched the geotechnical models necessary for sustainable mining (e.g., rational exploitation, the optimization of productivity, and zero accidents) including the planning of future reclamation.