The delicate interplay of various Earth’s systems processes in the Critical Zone is vital in ensuring an equilibrium across the different spheres of life. The upper crust forms a thin veneer on the Earth’s surface that is defined by an interconnected network of brittle structures. These brittle structures enable various Earth System processes. Increased anthropogenic interactions within the very upper crust have seemingly resulted in a growing number of negative natural effects, including induced seismicity, mine water drainage and land degradation. Brittle structures across South Africa are investigated. These structures include various fractures and dykes of different ages and geodynamic evolutions. The orientation of these structures is compared to the underlying tectonic domains and their bounding suture zones. The orientations corroborate an apparent link between the formation of the brittle structures and the tectonic evolution of the southern African crust. Reactivation and the creation of new structures are also apparent. These are linked to the variability of the surrounding stress field and are shown to have promoted magmatism, e.g., Large Igneous Provinces, and the movement of hydrothermal fluids. These fluids were commonly responsible for the formation of important mineral deposits. The preferred structural orientations and their relationship to underlying tectonic zones are also linked to fractured groundwater aquifers. Subsurface groundwater displays a link to structural orientations. This comparison is extended to surficial water movement. Surface water movement also highlights an apparent link to brittle structures. The apparent correlation between these Earth’s systems processes and the interconnectivity developed by brittle structures are clear. This highlights the importance of high-resolution geological and structural mapping and linking this to further development of the Earth’s Critical Zone.