Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including)eta(2)-allyl, aryl, and OR groups binding to Ag(I). AgSbF6 gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag2L2 capsule dependent on reaction stoichiometry and reaction conditions. Isostructural coordination chain structures are found with AgBF4 and AgClO4, while use of Ag(CF3SO3) gives two-dimensional (2-D) and 3-D coordination polymers through bridging triflate anions.