A new microwave-assisted extraction (MAE) method has been investigated for the extraction of phenolic compounds from rice grains. The experimental conditions studied included temperature (125–175 °C), microwave power (500–1000 W), time (5–15 min), solvent (10–90% EtOAc in MeOH) and solvent-to-sample ratio (10:1 to 20:1). The extraction variables were optimised by the response surface methodology. Extraction temperature and solvent were found to have a highly significant effect on the response value (p < 0.0005) and the extraction time also had a significant effect (p < 0.05). The optimised MAE conditions were as follows: extraction temperature 185 °C, microwave power 1000 W, extraction time 20 min, solvent 100% MeOH, and solvent-to-sample ratio 10:1. The developed method had a high precision (in terms of CV: 5.3% for repeatability and 5.5% for intermediate precision). Finally, the new method was applied to real samples in order to investigate the presence of phenolic compounds in a wide variety of rice grains.