Single crystals of the d-electron antiferromagnetic metal V5S8 can be prepared by chemical vapour transport with gaseous iodine as a transport agent. We present the outcomes of an endeavour to synthesise high-purity single crystals of V5S8 with reduced crystalline disorder, important to the formation of novel quantum orders. We report results on the residual resistivity ratio of the single crystals as growth parameters are varied including growth temperature, temperature gradient and pre-growth processing of the initial apparatus and reagents. We demonstrate that single crystals of at least a few mm in size can be successfully grown at relatively low temperatures in the range 550–600 °C. The optimisation of this method may imply a better crystallographic organisation, reducing sulphur vacancies and increasing vanadium positional order. The resulting longer electron mean free paths may enhance the probability of finding exotic quantum states of matter at low temperatures. The results presented here may also be of relevance to the development of vanadium sulphide-based energy storage and spintronic devices.