Coffee is one of the most popular beverages around the world. As one of the best-known coffee species, Liberian coffee (Coffea liberica Bull ex Hiern 1876) has a high resistance to leaf rust, a devasting disease caused by Hemileia vastatrix. However, there are few reports on the systematic position and phylogenetic relationship of C. liberica at the chloroplast (cp) genome level. Thus, we successfully assembled its cp genome. The full length is 154,799 bp with a GC content of 37.48%. We have further annotated the cp genome and predicted 85 protein-coding genes together with 8 rRNAs and 37 tRNAs. Furthermore, a large single copy region (LSC), a small single copy region (SSC), an inverted repeat region a (IRa) and an inverted repeat region b (IRb) are identified with lengths of 84,868 bp, 18,121 bp, 25,905 bp and 25,905 bp, respectively. The phylogenetic tree indicates that C. liberica is closely related to C. canephora, which is consistent with a previous result obtained from genotyping‐by‐sequencing.

The quality of different coffee varieties varies, and the corresponding bioactive value of coffee processing byproducts is often overlooked. For that, we employed HPLC, GC-MS, and electronic sensory analyses to evaluate the key bioactive components, antioxidant potential, and flavor traits of green coffee bean and coffee processing byproducts of seven coffee varieties. The results showed that green coffee beans (Oe+Ie) and exocarp (Ep) possessed strong antioxidant activity and high total phenolic content (TPC), caffeine and trigonelline content. Among the varieties, DR390 contained higher levels of total phenols, caffeine, and trigonelline, whereas DR402 was rich in caffeine and chlorogenic acid. In addition, RY3 exhibited higher TPC, total flavonoid content (TFC), caffeine, and chlorogenic acid. The parchment (Pc) layer was rich in soluble sugars (1.83–5.43%), while the silverskin (Sk) contained relatively high levels of chlorogenic acid (3.58–4.69 mg/g). Flavor analysis identified eleven classes of volatile compounds in green coffee bean (Oe+Ie) and byproducts (Ep, Pc, Sk), with esters, ketones, alcohols, and aldehydes being the most prevalent. Seven key aroma compounds, including methyl salicylate, phenethyl alcohol, nonanal, and benzaldehyde, were identified across the various structural tissues of coffee fruit. Distinct flavor profiles were observed among the coffee fruit parts: green coffee bean (Oe+Ie) was nutty; the Ep showed fruity and cocoa-like aromas; the Pc and Sk exhibited papery and nutty aromas, respectively. Varieties DR397, DR402, and RY3 exhibited pronounced aroma profiles. Comprehensive analysis showed that DR402 and RY3 had higher overall scores for bioactive and flavor components than other varieties in their groups. In summary, green coffee bean (Oe+Ie) exhibited strong antioxidant activity and high levels of bioactive compounds. Coffee byproducts, such as the Ep, hold potential for extracting natural antioxidants and bioactive compounds to develop specialty products or for other high-value utilization.