A novel silver(I) coordination polymer of I-methylpyrene (mpyr) with double-decker motifs, {[Ag-2(mpyr)(2)(ClO4)(2)]0.5benzene}(n) (1), was synthesized and characterized. Polymer I consists of I-D double-decker chains, which are formed by dimeric double-decker units ([Ag(mpyr)(ClO4)](2)) through the linkage of the perchlorate groups. In addition, the dimeric moieties between the adjacent chains are stacked to lead to column π-π stacks. Therefore, complex 1 can also be regarded as a 2-D stacking polymer, The effects of substituting groups, and other factors, on the structure of silver(I) complexes with polycyclic aromatic hydrocarbons are also discussed. [GRAPHICS]