We present a comprehensive study of the solid solution system Ca-2(MoO4)(2)-NaGd(MoO4)(2) on the molecular scale, by means of site-selective time resolved laser fluorescence spectroscopy (TRLFS). Eu3+ is used as a trace fluorescent probe, homogeneously substituting for Gd3+ in the solid solution crystal structure. Site-selective TRLFS of a series of polycrystalline samples covering the whole composition range of the solid solution series from 10% substitution of Ca2+ to the NaGd end-member reveals it to be homogeneous throughout the whole range. The trivalent ions are incorporated into the powellite structure in only one coordination environment, which exhibits a very strong ligand-metal interaction. Polarization-dependent measurements of a single crystal of NaGd(Eu)(MoO4)(2) identify the coordination geometry to be of C-2v point symmetry. The S-4 symmetry of the Ca site within the powellite lattice can be transformed into C-2v assuming minor motion in the first coordination sphere.