Rosmarinus officinalisleaves (ROLs) are widely used as a popular culinary spice for flavoring food, in which carnosic acid (CA) and rosmarinic acid (RA) are the main active components. The extraction of CA and RA is limited by lowextraction efficiency and extraction rate. In this work, a microwave-assisted extraction (MAE) method using biodegradable, low-toxic and nonflammable solvents polyethylene glycols (PEGs) as extraction solvents was developed for theextraction of CA and RA from ROLs. Experimental results suggest that PEG-400 was a better choice compared with PEG-200, and the optimal extraction conditions were as follows: 45% of PEG-400, 4.3% of phosphoric acid, 20 s of microwave irradiation time at 280 W of microwave irradiation power, and a 10 mg mL−1solid–liquid ratio, respectively. The tissue structures of ROLs could be effectively disrupted by PEG-based MAE, leading to high CA and RA extraction efficiencies. The PEG-400 extract exhibited stronger 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging ability compared with butylated hydroxytoluene (BHT). Finally, compared with heating reflux extraction, ultrasound-assisted extraction, maceration, and MAE using ionic liquid and ethanol as extraction solvents, the developed PEG-400 based MAE exhibited the highest extraction ability and fastest extraction rate for CA and RA. These findings suggest that MAE using PEGs as extraction solvents is a promising method for the separation of bioactive compounds from natural plants.