The compound Chinese herbal medicine (CCHM) is one of the most commonly used types of synergistic herbal medicine. It is based on composite herbal formula (CHF), which makes quality evaluation of this kind of traditional Chinese medicine (TCM) difficult. Taking Nvjin Pills (NJP) as an example, this study reported the development of a novel principle of analysis in CCHM. In order to improve the effectiveness of marketed drugs related active ingredients, it was necessary to designate a more unified quality evaluation standard. The core of the experimental is to prepare 3 batches of TCM reference drugs (TCMRD) using high-quality Chinese materia medica (single Chinese herbals used in the NJP). The active ingredients identified in the herbal formula including glycyrrhizic acid, cinnamaldehyde, paeonol, baicalin, hesperidin, paeoniflorin and ferulic acid were analyzed in both 3 TCMRDs and 76 batches of commercial products from 19 manufacturers by high performance liquid chromatography (HPLC) method combined with wavelength switching. NJP is a well-known Chinese patent medicine that has been widely applied for the clinical treatment of polycystic ovarian syndrome (PCOS) and other gynecological diseases. For the first time, the relationship between the components mentioned above and their pharmacological in the treatment of PCOS was explored via network pharmacology analysis. The simple prediction results of network pharmacological analysis verified the feasibility and reliability of the established quantitative analysis method for 7 compounds in NJP, which were recommended as candidate indicators for quality evaluation ultimately. Using the TCMRD as the scientific ruler, quality grade specifications of NJP were proposed by comprehensive analysis of multiple index. Accordingly, 16, 47, and 13 batches of samples were primarily rated as first-grade, second-grade and unqualified grade respectively. This study will provide a chemical basis for quality control of NJP, which is necessary in the production process of pharmaceutical development.