Sodium transition metal oxides are one of the most promising cathode materials for future sodium ion batteries. Chemical flexibility of layered Na-oxides including cobalt enables its partial substitution by other redox-active or non-active metals, often leading to structural stabilization. Sharing the same structural positions with other transition metals in layered oxides, Co can be double- or triple-charged, and as Co³⁺ can adopt a low-spin (LS), intermediate-spin (IS), high-spin (HS) state, or a combination of them. Using Ti⁴⁺ in the structure together with Co²⁺ results in a reduced number of phase transformations compared to Ti-free compositions. However, a large potential hysteresis of about 1.5–2.5 V between battery charge and discharge is observed, pointing a first-order cooperative phase transition. Based on several examples, we found that Na extraction from Na_xCo_x/2Ti_1−x/2O₂ materials with high-spin HS-Co²⁺, crystallizing in the P2 or O3 structure, mostly results in valence and spin-state transition of Co, leading to the formation of a second phase with a low-spin LS-Co³⁺, and a much smaller unit cell volume. We elucidated a kinetic origin of the potential hysteresis, which can be minimized by increasing temperature or reduction of the current density during battery cycling with P2- and O3-Na_0.67Co_0.33Ti_0.67O₂ materials. The slow kinetics of the structural phase transition, especially upon Na-insertion, hampers the application of classical methods of electrochemical thermodynamics, such as determining the entropic potential dE/dT. We showed that the entropic potential depends only on the Na-content in Na_xCo_0.33Ti_0.67O₂ during battery charge or discharge, what additionally confirms a kinetic nature of the potential hysteresis.