Zero-strain electrode materials that exhibit extremely small volume changes during intercalation reactions provide unique opportunities for highly stable lithium batteries. In particular, intecalation-induced strain in electrodes is a major factor in the degradation of advanced lithium batteries. For example, recent studies of high-performance Ni-rich layered cathodes unequivocally show a clear correlation between particle fracture, due to anisotropic volume expansion of polycrystalline grains, and continuously increasing cathode impedance.[1] Such chemo-mechanical behavior of electrode materials is even more critical to all-solid-state batteries in which the solid-solid interface between the electrode and solid electrolyte is prone to cracking and disintegration, even with small volume mismatches during electrochemical cycling. The best known zero-strain electrode material is the Ti-based spinel, Li4Ti5O12, that has been developed as a stable anode. Recently, LiRh2O4 spinel has been reported as a zero-strain cathode that operates at 3.2 V vs. Li/Li+,[2] however, its practical use is limited by the high cost of the precious metal, rhodium. A more feasible zero-strain cathode candidate is the ‘low-temperature’ (LT) form of LiCoO2, which adopts a cubic, lithiated spinel structure, Li2[Co2]O4.[3,4] On lithium extraction, LT-LiCoO2 provides an attractive 3.6 V vs Li. However, despite the high operating voltage and minimal volume change, this zero-strain material has received little attention since its discovery because of its poor cycling stability. In this presentation we report that cation substitution greatly improves the electrochemical perperties of LT-LiCo1-xMxO2 electrodes (M = cations). The different effects of various cation substituents on electrode performance will be compared and the zero-strain intercalation mechanism in LT-LiCo1-xMxO2 will be discussed.