1,3-Di(2-pyridyl)benzene undergoes regioselective orthometalation with Pd(OAc)2 on the central aryl ring, giving rise to a dimeric complex in which four acetate units act as bridges between two doubly metalated ligands and each pyridine ligand coordinates to a different metal atom. The reaction with chloride-containing Pd(II) complexes does not lead to C−H activation but to coordination complexes without Pd−C bonds. Cycloplatination of 1,3-di(2-pyridyl)benzene takes place at C-2 of the benzene ring, generating a terdentate ligand. This behavior is the same as that previously observed for Ru and Os. Both orthometalated complexes have been structurally characterized by X-ray diffraction.