The transition to low-carbon energy systems relies heavily on the development of advanced power electronics that combine high energy efficiency with compact design and thermal robustness. In this context, 4H-silicon carbide (4H-SiC) has emerged as a key wide band gap semiconductor, owing to its wide band gap (~3.26 eV), high thermal conductivity, and high critical electric field. These intrinsic properties make 4H-SiC particularly suitable for high voltage, high-frequency, and high-temperature applications, including electric vehicles, photovoltaic inverters, and data center power modules. However, the practical implementation of 4H-SiC-based devices is still limited by crystalline defects, doping inhomogeneities, and surface irregularities that affect carrier mobility, breakdown behavior, and long-term reliability. In this work, we employ advanced Atomic Force Microscopy (AFM) techniques—namely Scanning Spreading Resistance Microscopy (SSRM) and conductive AFM (c-AFM)—to probe the local electrical and morphological properties of 4H-SiC substrates, thin films and device layers at nanometric resolution. These techniques allow simultaneous characterization of topography, local conductivity, and dopant distribution, and enable the detection of subtle variations in electrical activity linked to structural features such as terraces, risers, and defects. A particular focus is given to the analysis of step bunching phenomena, modeled statistically to establish a quantitative relationship between crystallographic orientation and local electrical conductivity. Furthermore, a novel methodology has been developed to spatially resolve doping profiles, allowing both the identification of n- and p-type regions and the estimation of dopant concentration gradients within complex device architectures. Additionally, c-AFM was used to investigate local anodic oxidation phenomena, shedding light on electrochemical reactions at the nanoscale, with potential implications for surface passivation and interface engineering. Overall, this study provides new insights into the structure–property–performance relationships in 4H-SiC and contributes to the development of robust, defect-tolerant design strategies for next-generation power electronic devices.