A new family of vanadium-substituted chromium sulfides (V xCr2-xS3, 0 < x < 2) has been prepared and characterized by powder X-ray and neutron diffraction, SQUID magnetometry, electrical resistivity, and Seebeck coefficient measurements. Vanadium substitution leads to a single-phase region with a rhombohedral Cr 2S3 structure over the composition range 0.0 < x = 0.75, while at higher vanadium contents (1.6 < x = 2.0) a second single-phase region, in which materials adopt a cation-deficient Cr 3S4 structure, is observed. Materials with the Cr 2S3 structure all exhibit semiconducting behavior. However, both transport and magnetic properties indicate an increasing degree of electron derealization with increasing vanadium content in this compositional region. Materials that adopt a Cr3S4-type structure exhibit metallic behavior. Magnetic susceptibility data reveal that all materials undergo a magnetic ordering transition at temperatures in the range 90-118 K. Low-temperature magnetization data suggest that this involves a transition to a ferrimagnetic state. © 2008 American Chemical Society.