Prismatic crystals of Ag3(4-Amba)2(NO3)2 (I) and Ag(4-AmbaH)NO3 (II) are isolated from the reaction mixture of aqueous solutions of 4-aminomethylbenzoic acid (4-AmbaH) and AgNO3 at Т ≈ 70°C. The crystal structure of compound I (СIF file CCDC no. 1851513) and the luminescence properties of compounds I and II are studied. The structure of compound I contains two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) with the octahedral coordination mode (with allowance for Ag···Ag contacts) with different compositions of the internal spheres of the central atoms. Owing to the contacts, the silver atoms are joined into infinite cluster ribbons (Ag···Ag 3.06−3.27 A). The carboxylate group of the 4-Amba anion exhibits the bridging properties and binds the silver atoms of both types. The Ag(2) atoms also contact with the oxygen atom of the $${\text{NO}}_{{\text{3}}}^{-}$$ ion and coordinate the NH2 group of 4-Amba. The photoluminescence spectra of compounds I and II are of the same type and show the presence of two groups of emission bands with centers at 484 and 543 nm shifted to the red range of the spectrum relative to the band of 4-AmbaH.