The design and synthesis of a sterically hindered pyridine, 2,6-dimesitylpyridine, and its complexation of silver(I) salts is presented. X-ray crystal structural analysis of the light-stable bis(2,6-dimesityl)pyridine/silver(I) triflate complex clearly shows that the two pyridine ligands are mutually perpendicular, and the flanking mesityl groups thus effectively encapsulate the silver cation.