To attain chemical descriptors responsible for sensory characteristics linked to the botanical origin of five Brazilian coffee genotypes, a chemical survey was carried out. Highest and lowest amounts of caffeine were found in Apoatã and Obatã. Coffea dewevrei showed the lowest contents of 5-CQA and 3-CQA. 3,5-diCQA was higher for Apoatã and minimum values were detected in Icatu. Apoatã showed the highest contents of 3,4-diCQA and 4,5-diCQA, Catuaí, Icatu and Obatã revealed lower values of 4,5-diCQA. Among hydroxycinnamic acids ferulic acid prevailed in all genotypes, with lower values in Icatu and Obatã. 3,4-DCA remained significantly higher in Apoatã, C. dewevrei and Catuaí. Caffeic acid and p-coumaric acid did not vary significantly. It was concluded that Apoatã was most adequate for the decaffeinated industry; Catuaí, Icatu and Obatã were identified as producers of good beverages. Apoatã and C. dewevrei seemed to share closer parental origins to Coffea canephora cv. Robusta, whereas Icatu, Obatã and Catuaí showed higher similarities to Coffea arabica.