The two‐dimensional (2D) cluster‐based silver(I) complex {[Ag2(μ3‐L1)2(μ2‐HL1)]·H2O·3NO3}n (1) was isolated under hydrothermal conditions using the multi‐dentate triazole derivative ligand 4‐(4‐aminobenzene)‐1, 2, 4‐triazole (L1) and the corresponding silver(I) salts. The results indicate that 1 is constructed by tetranuclear AgI clusters as secondary building blocks. Each tetranuclear AgI cluster links four neighboring AgI clusters by eight bridging μ3‐L1 ligands forming a two‐dimensional (2D) microporous cluster‐based framework. Compound 1 also represents a scarcely reported example of coordination frameworks with 4‐(4‐aminobenzene)‐1, 2, 4‐triazole. The solid‐state fluorescence spectrum of 1 exhibits strong red‐shifted enhanced photoluminescence emission in comparison with that of free L1. The versatile bidentate and tridentate coordination modes of L1 in 1 together with flexible dihedral angles between aromatic benzene and triazole rings also reveal great potential in the construction of functional frameworks with L1.