We herein report the formation of the cyclic dimeric silver(I) complexes and the selective organic guest recognition. The reaction of pillar[5]-bis-crown with AgPF6 afforded a cyclic dimeric supramolecular complex [Ag4(L)2(H2O)2(CH3CN)2](PF6)4 in which the silver(I) atoms exist inside the crown ether cavities. The cyclic dimeric silver(I) complex reacts with 1,2-dicyanoethane (C2) to form a guest-inclusion complex [Ag4(C2@L)2(CH3CN)2](PF6)4, exhibiting its formation being controlled by the length of the guest molecules used. Additionally, the silver(I) supramolecular complex demonstrated molecular recognition for C2 in both solution and solid states.