Malvaceae plants have been reported to produce a wide range of structurally varied fatty acids. Therefore, in this work, the fatty acid content of Malvaviscus arboreus Cav. leaves was investigated using gas chromatography-mass spectrometry (GC‒MS) technique. A total of 17 fatty acids were characterized, with noticeable abundance of saturated acids (50.98%) that were principally dominated by palmitic acid (32.15%). Moreover, a number of mono-, di-, and tri-unsaturated fatty acids were detected constituting 24.92% of the total identified acids, of which 5,12-octadecadienoic acid (7.66%) was the major unsaturated acid identified. As a common feature of several genera of the Malvaceae family, some unusual fatty acids were identified from the saponifiable fraction of M. arboreus leaves, namely 9-methyl tetradecanoic, 3-methoxy pentadecanoic, and 9-heptadecynoic acids, that along with tetracosanoic, 9-octadecenoic, 13-octadecenoic, 5,12-octadecadienoic, and 9,11,15-octadecatrienoic acids, were also interestingly reported herein for the first time in the genus Malvaviscus.