We have successfully synthesized bulk single crystals of S0.66(2)WS2 using a topochemical method, confirming the successful intercalation of sulfur into the interlayer space of M-WS2, which induces hole doping. The material exhibits superconductivity with a transition temperature of 6.5 K, making it the first anion-intercalated/hole-doped TMD material. This innovative approach to achieving hole doping through anion intercalation offers significant potential for application to other TMDs, enabling better control over their properties and potentially uncovering new quantum phenomena. This work marks a major step forward in the exploration and modulation of TMD-based materials.