In conclusion, we revealed the complicated and intriguing Li + and Na + co-intercalation and ion exchange behavior in layered oxides. The two-phase equilibrium between Li0.94CoO2 and Na0.48CoO2 can be harnessed to guide the understanding of the ion (de)intercalation pathways. We unveiled that the relative kinetics of intercalation and ion exchange is crucial to determine the Li + extraction capacity, selectivity, and reversibility. We define an average ion exchange rate CpseudoIX to quantitatively compare the kinetics and divided the different intercalation behaviors into three regimes with CpseudoIX > Cinter (Regime 1), CpseudoIX ~ Cinter (Regime 2), and CpseudoIX < Cinter (Regime 3). The ion pathways for different regimes are constructed and illustrated clearly using the phase diagram of CoO2-LiCoO2-NaCoO2 by correlating the electrochemical response with in situ XRD and composition data. In regime 1 when CpseudoIX > Cinter, high vacancy Li phases are maintained, and the ion pathway can be kept for Li + intercalation to achieve the largest intercalation capacity and high Li selectivity without the assistance of ion exchange. By choosing the right particle running in Regime 1, the layered cobalt oxide demonstrated a 9.7×10 Li + selectivity and produced recovery solution with 99% Li + purity using 115 mAh/g capacity per recovery sequence with good reversibility. Interestingly, (LiNa)1-vCoO2 can benefit from an autointercalation phenomenon that favored Li + over Na + to enable FE > 100%. Our results show promise to enable the large class of layered oxides for Li + extraction to solve the Li supply chain concerns.