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Replacing harmful organic solvents that caused environmental pollution with an alternative medium for the development of ideal synthetic strategies is one of the primary focal points of green chemistry. Utilizing polyethylene glycol (PEG) as a nonvolatile solvent and promotor for the evaluation of safe processes has made a considerable contribution to the reduction of pollution problems. The current review summarizes the recent well-known catalyst-free organic reaction performed in polyethylene glycol as a green and biocompatible reaction medium.