The atomically controlled transition of nanohybrids and their effects on charge-carrier dynamics are highly desirable for fundamental studies in photocatalysis. Herein, for the first time, a method combining atomic monodispersity and single-atom alloy was used to prepare a new form of highly efficient silver-based cocatalysts (Ag25 & Pt1Ag24) on graphitic carbon nitride, representing a novel photocatalytic system for hydrogen evolution.