Enhancement of an alkaline water splitting reaction in Pt‐based single‐atom catalysts (SACs) relies on effective metal‐support interactions. A Pt single atom (PtSA)‐immobilized three‐phased PtSA@VP‐Ni3P‐MoP heterostructure on nickel foam is presented, demonstrating high catalytic performance. The existence of PtSA on triphasic metal phosphides gives an outstanding performance toward overall water splitting. The PtSA@VP‐Ni3P‐MoP performs a low overpotential of 28 and 261 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at a current density of 10 and 25 mA cm−2, respectively. The PtSA@VP‐Ni3P‐MoP (+,−) alkaline electrolyzer achieves a minimum cell voltage of 1.48 V at a current density of 10 mA cm−2 for overall water splitting. Additionally, the electrocatalyst exhibits a substantial Faradaic yield of ≈98.12% for H2 and 98.47% for O2 at a current density of 50 mA cm−2. Consequently, this study establishes a connection for understanding the active role of single metal atoms in substrate configuration for catalytic performance. It also facilitates the successful synthesis of SACs, with a substantial loading on transition metal phosphides and maximal atomic utilization, providing more active sites and, thereby enhancing electrocatalytic activity.