VOCl3 reacts with the thioethers RS(CH2)2SR (R = Me, Et or iPr) and 1,4-dithiane to form the first examples of VV thioether complexes, the highly reactive, intensely coloured [VOCl3(dithioether)] which have been characterised by 1H and 51V NMR, IR and UV/Vis spectroscopy. Combining VOCl3 with [9]aneS3 gives [VOCl3(2-[9]aneS3)] which, upon treatment with SbCl5 gives [VOCl2(3-[9]aneS3)][SbCl6]. Vanadium K-edge extended X-ray absorption fine structure (EXAFS) studies on three examples provided partial structural analyses for these very unstable compounds. Reaction of VCl4 with O(SiMe3)2 in CH2Cl2/MeCN followed by addition of RS(CH2)2SR (R = Me or Et) produced [VOCl2{RS(CH2)2SR}]. The crystal structure of [{VOCl2(MeSCH2CH2SMe)}4] reveals a unique tetrameric V4O4 core with each vanadium also coordinated to a chelating dithioether and two Cl ligands to complete the distorted octahedral geometry. Under rigorously anhydrous conditions VCl4 reacts with RS(CH2)2SR (R = Me, Et, iPr, Ph), 1,4-dithiane or [9]aneS3 to form [VCl4(thioether)] which are assigned as six-coordinate distorted octahedral species on the basis of their spectroscopic characterisation. In some cases trace hydrolysis of these compounds provides an alternative route to the [VOCl2(dithioether)] complexes.