AbstractLead halide perovskite (LHP) have gained considerable research attention for their numerous photoelectric applications attributed to their ease of processability and distinctive photoelectric properties. A‐site cation engineering provides an effective solution to optimize the bandgap further, enhance stability, and improve the photoelectric properties of LHP materials. In this review, an in‐depth examination of the progress achieved in the field of A‐site cation engineering on the structure, properties, synthesis methods, and photoelectric applications of LHP is presented. It is discussed how A‐site cations can change the crystal structure and improve the crystal quality, and how the A‐site cation regulates the bandgap, enhances stability, and promotes effective charge transport. Further, synthesis strategy is presented to regulate the A‐site cation. Subsequently, the applications of A‐site cation‐regulated LHP materials in solar cells, light‐emitting diodes, photodetectors, and lasers are introduced. Finally, challenges that must be overcome to further improve the properties and stability of LHP materials via A‐site cation engineering are highlighted.