Mechanochemical‐assisted extraction (MCAE) method was developed to an effective method for polysaccharides extraction from Ganoderma lucidum spores. The MCAE parameters and the antioxidant activity of polysaccharides were investigated. Through response surface methodology design experiments, the processing conditions were optimised as follows: material/solid reagent (Na2CO3) 5 g·g−1, milling time 20 min, solution/material ratio twenty (mL·g−1) and extraction time 130 min. Under these conditions, the yield of polysaccharides was (5.92 ± 0.13)%, which was in close agreement with the predicted value. Compared with the heat‐reflux extraction method, the MCAE method had higher extraction yield, shorter extraction time and lower extraction temperature. In addition, the polysaccharides obtained from MCAE exhibit significant antioxidant activity.