High energy density, nickel (Ni)-rich, layered LiNi x Mn y Co z O2 (NMC, x ≥ 0.6) materials are promising cathodes for lithium-ion batteries. However, several technical challenges, such as fast capacity fading and high voltage instability, hinder their large-scale application. Herein, we identified an optimum calcining temperature range for the Ni-rich cathode LiNi0.76Mn0.14Co0.10O2 (NMC76). NMC76 calcined at 750–775 °C exhibits a high discharge capacity (~215 mAh g−1 when charged to 4.5 V) and retains ca. 79% of its initial capacity after 200 cycles. It also exhibits an excellent high-rate capability, delivering a capacity of more than 160 mAh g−1 even at a 10 C rate. The high performance of NMC76 is directly related to the optimized size of its primary particles (100–300 nm) (which constitute the spherical secondary particles of >10 µm) and cation mixing. Higher calcination temperature (≥800 °C) leads to rapid increase of primary particle size, poor cycling stability, and inferior rate capability of NMC76 due to severe micro-strain and -crack formation upon repeated lithium-ion de/intercalations. Therefore, NMC76 calcined at 750–775 °C is a very good candidate for the next generation of Li ion batteries.