In recent years, as a green renewable energy production technology, electrochemical water splitting has demonstrated high development potential. Many materials have been reported as successful catalysts in the water-splitting field. However, it is still a huge challenge to produce bifunctional electrocatalysts for the efficient and sustainable generation of hydrogen and oxygen simultaneously. Herein, we successfully developed oxygen vacancies abundant CuCo layered double oxide (O_v-CuCo-LDO) hollow nanotube arrays (HNTAs) loaded on nickel foam as advanced electrocatalysts for total water splitting. When the current density was 10 mA cm⁻², the O_v-CuCo-LDO HNTAs exhibited outstanding onset overpotentials of 53.9 and 72.5 mV for the hydrogen evolution and oxygen evolution reactions (HER and OER) in alkaline medium, respectively, because of the bimetallic synergistic effect between the cobalt and copper and the unique hollow porous structure. In addition, an as-assembled O_v-CuCo-LDO||O_v-CuCo-LDO electrolytic cell showed a small potential of 1.55 V to deliver a current density of 10 mA cm⁻². Moreover, it also showed remarkable durability after long-term overall water splitting for more than 20 h. The research results in this paper are of great interest to practical applications of the water decomposition process, providing clear and in-depth insights into preliminary robust and efficient multifunctional electrocatalysts for overall water splitting.