Duckweeds are the smallest free-floating flowering aquatic plants. Their biotechnological applications include their use as food, bioenergy, and environmental sustainability, as they can help clean polluted water. The high growth capacity and their chemical properties make them suitable for human health applications. Here we evaluated the ethanolic extracts from five species of duckweeds by HPLC-DAD/MS-MS for chemical characterization. Sixteen compounds were identified and quantified, in which three were chlorogenic acid derivatives and eleven apigenin and luteolin derivatives. We describe for the first time the presence in duckweeds of 5-O-(E)-caffeoylquinic acid (1), 3-O-(E)-coumaroylquinic acid (2), luteolin-7-O-glucoside-C-glucoside (3), 4-O-(E)-coumaroylquinic acid (4), luteolin-6-C-glucoside-8-C-rhamnoside (5), and luteolin-8-C-glucoside-6-C-rhamnoside (6). The flavonoids diversity showed a significant content of luteolin and its derivatives, except for Landoltia punctata that had significant apigenin content. Flavones identified in duckweeds were mostly C-glycosides, which can benefit human diets, and its abundance seems to be related to the higher antioxidant and anticancer capacities of Wolffiella caudata, Wolffia borealis, and Landoltia punctata. Our findings reinforce the idea that duckweeds could be valuable additives to the human diet, and their potential should be further explored.