The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g−1 DMTS (1.66 A h L−1), which decreases to 59 mAh g−1 DMTS (0.75 A h L−1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g−1 sulfur (3.83 A h L−1), for which 1030.9 mAh g−1 sulfur (3.23 A h L−1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.