**Background:** Citri Reticulatae Pericarpium Viride (CRPV), known as "Qing Pi" in Chinese, is derived from the dried infancy fruit or immature peel of Citrus reticulata Blanco. The subtype "Geqingpi" (GQP) is collected in May and June and is used for dyspepsia, expectorant, asthma, and liver conditions. While extensive research has focused on the chemical components of mature Citri Reticulatae Pericarpium (CRP), systematic chemical profiling of CRPV, particularly GQP, has been lacking. This study aimed to comprehensively identify the volatile and nonvolatile chemical constituents of GQP using multiple analytical techniques.
**Methods:** GQP samples were collected from Xinhui District, Jiangmen, Guangdong Province in May 2020. Volatile constituents were extracted using steam distillation (30 g powder soaked in 300 ml water for 12 h, heated for 5 h) and analyzed by GC–MS (Agilent 7890A/5975C system with DB-5MS column). Nonvolatile compounds were extracted with methanol via ultrasonication (320 W, 40 kHz, 30 min) and analyzed by UHPLC‐Q‐Exactive Orbitrap‐MS (ZORBAX Eclipse Plus C18 column, 0.1% formic acid in water/acetonitrile gradient, positive ion mode). Seven bioactive components (synephrine, limonin, hesperidin, nobiletin, HMF, tangeretin, 5-HPMF) were quantified by HPLC–PDA at detection wavelengths of 209, 224, 283, and 330 nm.
**Key Results:** The extraction yield of volatile compounds from GQP was 1.18%. A total of 56 volatile constituents were identified, comprising 99.93% of all identified volatile constituents. These included 22 terpenes, 12 alcohols, 3 phenols, 2 ketones, 1 aldehyde, 5 esters, and 11 others. Terpenes were the predominant volatile components (approximately 70% relative content), with γ-terpinene (33.39%) and D-limonene (22.95%) being the most abundant. For nonvolatile compounds, 42 constituents were successfully separated and identified within 16 minutes by UHPLC‐Q‐Exactive Orbitrap‐MS, including 23 flavonoids (eight flavonoid glycosides, eight polymethoxyflavones [PMFs], and seven other flavonoids), nine organic acids, two alkaloids, three coumarins, and five other compounds. Nine compounds were reported for the first time in CRPV: vitexin, iristectorigenin, isoferulic acid, esculin, esculetin, 5,7-dimethoxycoumarin, 5-hydroxymethylfurfural, methyl ferulate, and ethyl4'-hydroxy-3'-methoxycinnamate. Quantitative HPLC–PDA analysis showed that GQP contained high concentrations of hesperidin (160.78 ± 0.95 mg/g), nobiletin (4.29 ± 0.02 mg/g), tangeretin (3.07 ± 0.01 mg/g), synephrine (5.57 ± 0.05 mg/g), limonin (4.11 ± 0.10 mg/g), 5-HPMF (0.51 ± 0.01 mg/g), and HMF (0.18 ± 0.004 mg/g). The method validation showed R² values >0.99 for all calibration curves, and RSDs for recovery, repeatability, stability, and precision were all less than 3.00%, with recovery ranging from 87.58% to 108.71%.
**Clinical Implications:** This comprehensive chemical profiling of GQP provides a detailed basis for quality control and further development of this traditional Chinese medicine. The exceptionally high hesperidin content (160.78 mg/g) far exceeds the Chinese Pharmacopoeia minimum requirement of 5.0%, suggesting potential therapeutic applications given hesperidin's lipid-lowering and insulin-sensitizing properties. The abundance of PMFs (nobiletin and tangeretin) and other bioactive compounds (synephrine, limonin) supports the traditional uses of GQP and provides a foundation for future pharmacological studies, particularly regarding antioxidant, anticancer, anti-inflammatory, and metabolic effects.