AbstractHerein described a highly efficient palladium‐catalyzed cascade desulfitative arylation of acetylinic oximes and sodium arylsulfinates with oxygen as the sole oxidant to access structurally diverse 4‐aryl isoxazoles. This catalytic system exhibits mild conditions, broad substrate scope, and operational simplicity. Notably, other easily available aryl source substrates were perfectly tolerated in this catalytic system, thus providing a promising application in synthetic and pharmaceutical chemistry.