<jats:p>Asperteramide A, an unusual <jats:italic>N</jats:italic>‐phenyl‐carbamic acid methyl ester trimer, was isolated and identified from the coral‐derived fungus <jats:italic>Aspergillus terreus</jats:italic>. The deceptive and indistinguishable NMR signals caused by three <jats:italic>N</jats:italic>‐phenyl‐carbamic acid methyl ester subunits located in different spatial environments created great challenge for the identification of its planar structure, but recrystallization ultimately afforded a suitable crystal for the X‐ray diffraction experiment, which enabled its final structure determination. The plausible biosynthetic pathway of <jats:bold>1</jats:bold> mainly involved in the successive Friedel–Crafts reactions. Additionally, compound <jats:bold>1</jats:bold> showed significant antibacterial activity against seven microbial pathogens [ESBL‐producing <jats:italic>Escherichia coli, Acinetobacter baumannii, Pseudomonas aeruginosa, Klebsiella pneumoniae</jats:italic>, methicillin‐resistant <jats:italic>Staphylococcus aureus, Enterococcus faecalis, Candida albicans</jats:italic>] with MIC values ranging from 2 to 64 µg/mL.