Palladium‐catalyzed Suzuki–Miyaura reaction is an important synthetic strategy for the synthesis of biaryl compounds. This work describes that palladium complexes with N,O‐bidentate ligands bearing N‐oxide units from cyclic secondary amines were used as highly efficient catalysts for Suzuki–Miyaura reactions of aryl halides with arylboronic acids. The reaction exhibited good functional group compatibility, high yields, and mild conditions. More importantly, these N,O‐coordinated palladium complexes could be easily prepared and displayed excellent catalytic performance for this classic Csp2–Csp2 coupling reaction in very short time.