<jats:title>Abstract</jats:title><jats:p>Roquefortine C (<jats:bold>1</jats:bold>) and 11‐bromoroquefortine C (<jats:bold>4</jats:bold>) were isolated from <jats:italic>Penicillium chrysogenum</jats:italic>, an endophyte obtained from green leaves of <jats:italic>Coffea arabica</jats:italic>, during induction experiments by adding halide salts to the culture media. In our studies, 11‐bromoroquefortine D and 11‐bromo‐17‐hydroxybromoroquefortine C were identified by LC/HR‐MS. It is the first time that bromoroquefortine C and D are described as halogenated natural products. These halo alkaloids were shown to be biosynthesized from brominated tryptophan as the biosynthetic precursor. Cytotoxic and antibiotic assays using roquefortine C and 11‐bromoroquefortine C showed that the presence of the 11‐Br substituent impairs some biological activities of this alkaloid.