This work describes the synthesis of two new benzoic nitrooxy derivatives of matrine (3-nitrooxymethylbenzoate and 4-nitrooxymethylbenzoate). Matrine was hydrolyzed under alkaline condition to give the ring-opening carboxylic acid derivative (matrine acid), and the coupling of nitrooxymethylbenzoyl group to the matrine acid was accomplished through amide linkage.