In this study, citric acid was applied as a safe organic acid for the treatment of the brown macroalga Sargassum latifolium to facilitate the sequential extraction of fucoidan and alginate without cross contamination. Box-Behnken experimental design was used to investigate the effects of citric acid concentration, temperature, and time on fucoidan yield, its fucose and sulfate contents, and molecular weight (MW), while the investigated responses of the sequentially extracted alginate were yield, mannuronic/guluronic acid ratio (M/G) and MW. Under the optimized conditions, the fucoidan yield, fucose content, sulfate content, and MW were 6.55%, 21.01%, 30.92% and 7.12 × 10³ Da, respectively, while alginate yield, M/G, and MW were 28.81%, 0.36, and 1.50 × 10⁵ Da, respectively. The optimized products showed good Fe(III) chelating properties and the iron contents were 509.82 mg g⁻¹ for fucoidan-Fe and 406.71 ± 5.18 mg g⁻¹ for alginate-Fe. Under simulated gastrointestinal conditions, fucoidan-Fe and alginate-Fe complexes released 46 and 57% iron, respectively, which are nutritionally relevant amounts. Both fucoidan and alginate showed potent antioxidant properties, but their Fe complexes exhibited a reduced activity. The results of the present study indicated that citric acid could support the basis for an economical biorefinery process for the sequential extraction of fucoidan and alginate. Additionally, these polysaccharides could be good candidates for the preparations of iron supplements.