Four organosilver(I) complexes of polycyclic aromatic hydrocarbons (PAHs) have been investigated crystallographically. The aim was to establish whether a favorable combination of cation-pi interactions and aromatic stackings might produce functional organometallic solid materials with novel networks. Complete structures of the silver(I) perchlorate with 9,10-diphenylanthracene (L-1), rubrene (L-2), benzo[a]pyrene (L-3), and coronene (L-4) were determined by X-ray diffraction. All compounds are organometallic species based on cation-pi interactions. While complex 1 with L-1 revealed a discrete mononuclear structure, complex 2 with rubrene displayed a ct-bonded 3-D polymer. Complexes 3 and 4 can be regarded as both coordination polymer and stacking polymer, and the detailed differences in the geometries and the stacking patterns of 1,3 and L-4 gave helical and triple-decker networks, respectively. The ESR spectroscopic results and conductivity of the compounds are also discussed. The present findings may serve as a basis for understanding specific interactions responsible for self-assembly of multinuclear aggregates involving PAHs.