Due to thegrowing awareness of fossil fuel depletion and environmental issues, biodiesel alternative fuel is currently of substantial interest. This research assessed herbal industry wastes as a potential resource for biodiesel production for the first time. Fatty acid methyl esters (FAMEs), obtained in the transesterification reaction, were extracted from the herbal samples by ultrasound-assisted extraction and identified withgas chromatography-mass spectrometry in the selected ion monitoring mode. The presence of at least 20 (e.g., in chamomile and chicory) FAMEs, up to 31 in nettle and senna, was reported. The unsaturated FAMEs were found in higher amounts than saturated. Linoleic acidwas the major polyunsaturated FAME in herbal wastes, while palmitic acid was the major saturated FAME. The highest content of FAMEs was identified in rye bran, Figure tea, and chicory. According to the cetane number prediction, BS EN 14214:2012+A2:2019, and hierarchical clustering on principal components (HCPC)wastes from, e.g., nettle, sage, and senna, are the most suitable in biodiesel production with fuel properties acceptable by the EuropeanStandards.Principal component analysis and HCPC allowed to classify and groupsimilar plants according to their FAMEs content; however, additional studies of herbal biofuel properties are needed.