Three novel silver(I) complexes with benzopyrene derivatives were synthesized and characterized in this paper. Treatment of AgClO4.H2O with 7-methylbenzo[a] pyrene (L-1) afforded [Ag-2(L-1) (toluene)(0.5)(ClO4)(2)](n) (1) which exhibits a 2-D sheet structure with double-stranded helical motifs. Reaction of AgCF3SO3 with dibenzo[b,def]chrysene (L-2) gave rise to an unprecedented cocrystallization structure, {[Ag-2(L-2)(CF3SO3)(2)][Ag-2(toluene)(2)(CF3SO3)(2)]}(n) (2)1 formed by a 2-D neutral lamellar polymer and a 1 D neutral rodlike one. The ligand benzo[e]pyrene (L-3) coordinated to silver(I) ions generating a closed triple-decker tetranuclear complex [Ag-4(L-3)(4)(p-xylene)(ClO4)(4)] (3) which can be regarded as a stacking polymer owing to existing intermolecular pi-pi stack interactions. The structural diversity of the silver(I) coordination polymers with polycyclic aromatic hydrocarbons is not only related to the stacking patterns of free polycyclic aromatic hydrocarbons in the crystalline state, but also the geometric shapes of the molecules for these free ligands. In addition, the coordination of solvents to metal ions plays a crucial role in the formation of the unprecedented coordination polymeric architectures. The ESR spectroscopic results, conductivity, and synthesis properties are also discussed.