The metal halide (BX 6 ) 4- octahedron, where B represents a metal cation and X represents a halide anion, is regarded as the fundamental structural and functional unit of metal halide perovskites. However, the influence of the way the (BX 6 ) 4- octahedra connect to each other has on the structural stability and optoelectronic properties of metal halide perovskite is still unclear. Here, the octahedral connectivity, including corner-, edge-, and face-sharing, of various Cs x FA 1-x PbI 3 (0 ≤ x ≤ 0.3) perovskite films is tuned and reliably characterized through compositional and additive engineering, and with ultralow-dose transmission electron microscopy. It is found that the overall solar cell device performance, the charge carrier lifetime, the open-circuit voltage, and the current density-voltage hysteresis are all improved when the films consist of corner-sharing octahedra, and non-corner sharing phases are suppressed, even in films with the same chemical composition. Additionally, it is found that the structural, optoelectronic, and device performance stabilities are similarly enhanced when non-corner-sharing connectivities are suppressed. This approach, combining macroscopic device tests and microscopic material characterization, provides a powerful tool enabling a thorough understanding of the impact of octahedral connectivity on device performance, and opens a new parameter space for designing high-performance photovoltaic metal halide perovskite devices.