LiNi0.95Al0.05O2 cathode materials have attracted much interest as lithium storage materials for rechargeable lithium batteries because of their high capacity and low cost. However, they exhibit poor cycling performance and thermal instability. We synthesized Li[Ni0.87Co0.08Al0.05]O2 as a shell with high structural and thermal stability on the core surface to suppress surface degradation while maintaining high capacity. The capacity retention of the core-shell cathode after 30 cycles was 87%, which was better than that of the bare cathode (73%). Differential scanning calorimetry analysis revealed that the heat generation of the core-shell cathode was 331.4 J·g−1, which was lower than that of the bare cathode (487.5 J·g−1).