Exploring highly active and inexpensive bifunctional electrocatalysts for water-splitting is considered to be one of the prerequisites for developing hydrogen energy technology. Here, an efficient simultaneous etching-doping sedimentation equilibrium (EDSE) strategy is proposed to design and prepare hollow Rh-doped CoFe-layered double hydroxides for overall water splitting. The elaborate electrocatalyst with optimized composition and typical hollow structure accelerates the electrochemical reactions, which can achieve a current density of 10 mA cm−2 at an overpotential of 28 mV (600 mA cm−2 at 188 mV) for hydrogen evolution reaction (HER) and 100 mA cm−2 at 245 mV for oxygen evolution reaction (OER). The cell voltage for overall water splitting of the electrolyzer assembled by this electrocatalyst is only 1.46 V, a value far lower than that of commercial electrolyzer constructed by Pt/C and RuO2 and most reported bifunctional electrocatalysts. Furthermore, the existence of Fe vacancies introduced by Rh doping and the typical hollow structure are demonstrated to optimize the entire HER and OER processes. EDSE associates doping with template-directed hollow structures and paves a new avenue for developing bifunctional electrocatalysts for overall water splitting. It is also believed to be practical in other catalysis fields as well.