The development of decarbonised systems is being fostered by the increasing demand for technological solutions for the energy transition. Solid Oxide Cells are high-efficiency energy conversion systems that are foreseen for commercial development. They exhibit potential power generation and power-to-gas applications, including a reversible operation mode. Long-lasting high performance is essential for guaranteeing the success of the technology; therefore, it is fundamental to provide diagnosis tools at this early stage of development. In this context, operando analysis techniques help detect and identify incipient degradation phenomena to either counteract damage at its origin or correct operando protocols. Frequent switches from the fuel cell to the electrolyser mode add more challenges with respect to durable performance, and deep knowledge of reverse-operation-induced damage is lacking in the scientific and technical literature. Following on from preliminary experience with button cells, in this paper, the authors aim to transfer the methodology to commercial-sized Solid Oxide Cells. On the basis of the experimental evidence collected on planar square cells under dry and wet reactant feed gases, the main contributions to impedance are identified as being charge transfer (f = 103−104 Hz), oxygen surface exchanged and diffusion in bulk LSCF (f = 102−103 Hz), and gas diffusion in the fuel electrode (two peaks, f = 1−100 Hz). The results are validated using the ECM methodology, implementing an LRel(RctQ)GWFLW circuit.