High-entropy oxides (HEOs), a class of compounds that include five or more elemental species, have gained increasing attraction for their capability of optimizing the target properties. To date, even though some high-entropy oxides have been successfully prepared, their applications still need to be explored. In the present study, a lithium-manipulation strategy for constructing transition metal oxides (LTM) via a modified solid-state method was investigated. The as-synthesized LTM contained six highly dispersed metal species (Li, Fe, Co, Ni, Cu, Zn) and demonstrated a rocksalt-type structure. Besides, with the introduction of Li, more oxygen vacancies were produced which was also accompanied by shrinking of the lattice constant. When the molar ratio of Li was equal to the other TM cations (LTM16.7), the electrical conductivity was greatly enhanced by a factor of 10 times. Moreover, LTM16.7 achieved the best HER (η = 207 mV at 10 mA cm⁻²) and OER performances (η = 347 mV at 10 mA cm⁻²) with elevated electrical conductivity. To facilitate further design of this new kind of materials, we also conducted DFT calculations and elemental alternation experiments, which showed that Fe acted as electrocatalytic sites in this HEOs system. This Li-incorporation strategy opens a new way to understand and modify defect-related HEOs.