cis,cis,cis‐1,2,3,4‐Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ efficiently catalyses the Suzuki reaction of heteroarylboronic acids with aryl bromides and also the coupling of arylboronic acids with heteroaryl bromides. The coupling of thiophene‐ or benzothiopheneboronic acids, furan‐ or benzofuranboronic acids and 3‐pyridineboronic acid with a variety of aryl bromides gave the corresponding coupling products in good yields. However, in most cases, better results in terms of ratio substrate/catalyst were obtained for the reverse reaction using heteroaryl bromides with arylboronic acids.