The electrodes that are inexpensive, had high catalytic activity, and can be easily produced in situ on a conductive substrate have been studied extensively to produce hydrogen through water splitting. Herein, a Co‐Fe layered double hydroxide (Co‐Fe LDH) and a metal‐organic framework (MOF)‐derived cobalt phosphide (CoP) are combined to fabricate a catalyst without any binders on a conductive carbon cloth (CC) that has abundant surface area and flexibility. The prepared electrode is then applied to the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in 1 M KOH electrolyte and the overpotentials necessary to reach 10 mA/cm² are 172 and 270 mV, respectively. Moreover, the Tafel slopes are 39 and 79 mV⁻¹ for OER and HER, respectively, thereby outperforming Co‐Fe LDH and CoP individually. The potential needed to reach 10 mA/cm² is 1.66 V in overall water splitting using the two‐electrode configuration. Notably, the catalytic activity is not degraded even after 50 hours of operation. Characterizations demonstrate that the combination of Co‐Fe LDH and CoP based on the catalyst and the strong coupling effect among the Co, Fe, and P active sites account for the excellent HER and OER performances. Our suggested in situ method represents a novel route for the preparation of hierarchical MOF‐derived CoP@Co‐Fe LDH (hierarchical CoP@Co‐Fe LDH) composite on conductive CC‐based high‐performance electrocatalysts for overall water splitting.