A series of new sterically hindered bridged ligand 4,4′-methylene-N,N′-bis(phenyl-2-pyridylmethylene)-bis(2,6-dialkylanil)s was efficiently synthesized by the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) and benzoyl pyridine. They easily coordinated with Ag(I) to form Ag(I) complexes. The structure of complex [Ag2L42][ClO4]2 was determined by the single X-ray crystallographic analysis, and the double-helical asymmetric unit containing two [Ag2L42] moieties was interconnected with the adjacent unit through hydrogen bonds to form a helical supramolecular architecture.