Vanadate ellestadites Ca-10(SiO4)(x)(VO4)(6-2x)(SO4)(x)Cl-2, serving as prototype crystalline matrices for the fixation of pentavalent toxic metals (V, Cr, As), were synthesized and characterized by powder X-ray and neutron diffraction (PXRD and PND), electron probe microanalysis (EPMA), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (SS-NMR). The ellestadites 0.19 < x < 3 adopt the P6(3)/m structure, while the vanadate endmember Ca-10(VO4)(6)Cl-2 is triclinic with space group P<(1)overbar>. A miscibility gap exists for 0.77 < x < 2.44. The deficiency of Cl in the structure leads to short-range disorder in the tunnel. Toxicity characteristic leaching testing (TCLP) showed the incorporation of vanadium increases ellestadite solubility, and defined a waste loading limit that should not exceed 25 atom % V to ensure small release levels.