Headspace ( HS ), extractive, and distillative methods were employed to isolate volatile and semivolatile compounds from fresh C offea arabica flowers. Static HS solid‐phase microextraction ( HS ‐ SPME ), microwave‐assisted HS ‐ SPME ( MW ‐ HS ‐ SPME ) with simultaneous hydrodistillation, and extraction with hexane or supercritical CO 2 ‐isolated mixtures in which around 150 different chemical substances were identified or tentatively identified by GC – MS analysis. n ‐Pentadecane (20–37% relative peak area, RPA ) was the most abundant compound in the HS fractions from fresh flowers, followed by 8‐heptadecene (8–20% RPA ) and geraniol (6–14% RPA ). Hydrocarbons (mostly C 13 – C 30 paraffins) were the predominant compound class in all the sorptive extractions ( HS ‐ SPME , MW ‐ HS ‐ SPME , distillate), followed by terpenoids or oxygenated compounds (which varied with the isolation technique). Caffeine, a distinctive component of coffee fruits and beans, was also found in relatively high amounts in the supercritical CO 2 extract of C . arabica flowers.