The influence of coffee cultivar, roasting degree and brewing procedure in the presence and transfer of caffeine and caffeoylquinic acids (CQAs) from ground roasted coffee to the brew was evaluated. Two coffee cultivars were roasted in three roasting degrees and brewed using two different procedures. Compounds were determined simultaneously by HPLC-DAD. Caffeine levels ranged from 87.3 to 122.5 mg/100 mL for Coffea arabica cv. Catuaí Amarelo and from 123.3 to 192.0 mg/100 mL for C. canephora cv. Apoatã. The sum of CQA isomers ranged from 24.2 to 41.3 mg/100 mL for brews prepared with dark roasted coffee and from 187.7 to 295.6 mg/100 mL for light roasted ones. Brews prepared by boiling showed higher content of the compounds than the corresponding filtered ones. C. arabica cv. Catuaí Amarelo light roasted coffee brew presented the lowest caffeine/CQA ratio, regardless of the brewing procedure used, in comparison with the highest ratio of the dark boiled brews.