The generation of spin currents from charge currents via the spin Hall effect (SHE) is of fundamental and technological interest. Here, some of the largest SHEs yet observed via extrinsic scattering are found in a large class of binary compounds formed from a 5d element and aluminum, with a giant spin Hall angle (SHA) of ≈1 in the compound Os22Al78. A critical composition of the 5d element is found at which there is a structural phase boundary between poorly and highly textured crystalline material, where the SHA exhibits its largest value. Furthermore, a systematic increase is found in the spin Hall conductivity (SHC) and SHA at this critical composition as the atomic number of the 5d element is systematically increased. This clearly shows that the SHE and SHC are derived from extrinsic scattering mechanisms related to the potential mismatch between the 5d element and Al. These studies show the importance of extrinsic mechanisms derived from potential mismatch as a route to obtaining large spin Hall angles with high technological impact. Indeed, it is demonstrated that a state‐of‐the‐art racetrack device has a several‐fold increased current‐induced domain wall efficiency using these materials as compared to prior‐art materials.