Rice high in resistant starch (RS) showed great benefits in preventing diabetes. Red mold rice (RMR) is a traditionally functional food in China, preparing RMR with high-RS rice might produce a novel RMR with better nutrients and promote the utilization of high-RS rice in the food industry. R4 with the highest RS content was the most prone to be fermented by Monascus. After fermentation, the total starch and protein contents were significantly decreased, while the RS, lipid, free glucan, total free amino acids (FAAs), and γ-aminobutyric acid (GABA) contents were remarkably increased. Concurrently, the phenolic content and antioxidation activity were enhanced greatly. The individual phenolic acids such as ferulic acid showed significantly positive correlations with the antioxidant activity. Besides the abundant lipids, FAAs, GABA, and strong antioxidant capacity, fermented R4 had the highest ferulic acid content. This study provided alternatives for producing novel RMR and widened applications of high-RS rice in innovative functional foods.