In order to study the charge effect on the formation of an anion-templated silver cluster, a trivalent tetrahedral anion was incorporated into the silver assembly. A 26-nuclear silver cluster was prepared, and its structure was confirmed by single-crystal X-ray diffraction. Also, the resulting structure was characterized by powder X-ray diffraction data. Its light absorption and photoluminescent properties were studied by solid-state UV diffuse-reflectance and fluorescence spectroscopy. Compared with the other reported silver clusters with tetrahedral anion templates, the more negative VO(4)(3-)anion led to the formation of a bigger silver cluster. Also, the supramolecular motif O-H(CH3OH)center dot center dot center dot O(trifluoro-acetate) was confirmed on the cluster surface for the first time.