A rare example of pentacoordinated silver(I) complex featured unconventional type of coordination of 8-phenylquinoline has been prepared. DFT calculations indicated that the silver(I) center forms two strong coordination bonds with the N atoms (21.8–29.8 kcal/mol) and an electrostatically provided bond with the triflate anion (the charges at the silver(I) center and the triflate O atom are estimated as +0.64 and −1.02 e, respectively). The coordination polyhedron is complemented by two semicoordination bonds with the C atoms of the phenyl rings (4.3–6.0 kcal/mol). These silver(I)–phenyl π-interactions are significantly stronger than such interactions observed previously for other systems exhibiting energy lower than 2 kcal/mol.