LiCoO2 (LCO) with average particle distribution of 8 ��m (LCO-A) and 11 ��m (LCO-B) exhibit substantial differences in cycle performance. The half-cells have similar first-cycle discharge capacities of 173 and 175 mAh/g at 0.25 C, but after 100 cycles, the discharge capacities are substantially different, that is, 114 and 141 mAh/g for LCO-A and LCO-B, respectively. Operando neutron powder diffraction of full LCO||Li4Ti5O12 batteries show differences in the LCO reaction mechanism underpinning the electrochemical behavior. LCO-A follows a purely solid solution reaction during cycling compared to the solid solution and two-phase reaction mechanism in LCO-B. The absence of the two-phase reaction in LCO-A is consistent with a homogeneous distribution of Li throughout the particle. The two-phase reaction in LCO-B reflects two distinguishable distributions of Li within the particles. The faster capacity decay in LCO-A is correlated to an increase in electrode cracking during battery cycles.