In this study, we have employed dithiooxamide, a solid, odorless, and commercially available compound, as a sulfur surrogate for the preparation of dialkyl sulfides from available alkyl halides in high yields. This sulfur transfer agent was also used for a copper‐catalyzed high‐yielding preparation of diaryl sulfides from their available aryl halides and for the preparation of thia‐Michael adducts in high yields. All the reactions were performed under odorless conditions in wet PEG200 (PEG = polyethylene glycol), which is an eco‐friendly, safe, and recoverable solvent. The protocols were easily applicable to large‐scale operation.