As a prevailing cathode material of lithium-ion batteries (LIBs), LiCoO2 (LCO) still encounters the tricky problems of structural collapse, whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling. Hereinafter, we propose a strategy using a zeolitic imidazolate framework (ZIF) as the self-sacrificing template to directionally prepare a series of LiNi0.1Co0.9O2 (LNCO) with tailorable electrochemical properties. The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage, during which the sample prepared at 700 °C (LNCO-700) outperforms its counterparts in cyclability (156.8 mA h g−1 at 1 C for 200 cycles in half cells, 1 C = 275 mA g−1) and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness. The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study, during which LNCO-700 (167 mA h g−1 at 1 C for 100 cycles in full cells) surpasses LCO-700 in battery performance due to the mitigated phase deterioration, stabilized layered structure, ameliorated electronic conductivity, and exalted lithium storage activity. This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.