The recent material research of mixed cobalt oxides is strongly motivated by the potential of some of them to be used as chemically stable high temperature thermoelectric material. This fact together with both the theoretical and experimental ambitions to fulfill the severe criteria needed for efficient thermoelectric conversion intensified both their theoretical and experimental research. Nonetheless, despite the investigations of the prototype materials represented by 3D perovskites Ln1−xAxCoO3 (Ln = La, Y, rare-earth, A = alkaline-earth) and 2D cobaltites of NaxCoO2 type, the concise physical background of their transport and magnetic properties remain still a matter of debate. This is likely due to a fact that cobalt ions can be stabilized either in low-spin state (diamagnetic for “pure” Co3+), with filled t2g levels and empty eg states, or magnetic ones, with filled eg states. As the energy difference between respective states is due to comparable strength of crystal field and Hund's energies rather small, the thermodynamically most stable ground-state, with eventually different character of charge carriers, can be critically influenced by an interplay of additional degrees of freedom - orbital and charge. The challenge for unequivocal theoretical model represents the thermoelectric power of mixed cobaltites where, up to now, somewhat ambiguous models based either on “classical” approach, associated with diffusion of itinerant charge carriers, or more exotic - based on configurational entropy of quasi-itinerant carriers - are often used for similar materials. Simultaneously, the open question remains the assessment of the dominant mechanism of phonon scattering in 2D cobaltites.