Metal-doped nanoporous carbon (MDNC) derived from core–shell metal–organic frameworks (MOFs) exhibits temperature-dependent thermoelectric behavior that is highly sensitive to nanoporous structure and surface interactions. In this study, a pellet-based approach is employed to enable systematic investigation of the Seebeck coefficient and electrical conductivity of MDNC as a function of temperature. Differential scanning calorimetry (DSC) reveals a pronounced desorption process in the temperature range of 80–100 ℃, which is closely correlated with significant changes in electrical transport properties. To further elucidate this behavior, MDNC samples with different particle sizes (~ 200 nm and ~ 800 nm) are examined, demonstrating distinct temperature-dependent variations in both Seebeck coefficient and electrical conductivity. These results indicate that temperature-induced desorption plays a critical role in modulating carrier transport through changes in interfacial barriers, scattering mechanisms, and conductive pathway connectivity. The particle-size-dependent nanoporous structure further influences this behavior by altering adsorption/desorption characteristics. Overall, this study provides insight into the coupling between nanoporous structure and temperature-dependent transport behavior in MDNC, offering a framework for understanding and tuning thermoelectric responses in nanoporous carbon systems.