Marine macroalgae biomass is a valuable renewable resource that can be used for the development of bioeconomy through the valorisation of valuable compounds. The aim of the current study is separate macroalgal polysaccharides with bioactive properties from brown macroalgae Fucus spiralis based on a designed biocascading biorefinery approach. Thus, we applied an integrated processing method for the separation of fucoidan and alginate, in addition to characterization through IR spectroscopy and ¹H NMR. The bioactivity potential (antioxidant activity using superoxide anion and DPPH radical scavenging analysis) of the two polysaccharides was evaluated, together with DNA binding studies performed though voltametric techniques and electronic spectroscopy titration. In terms of results, functional groups S=O (1226 cm⁻¹), N=S=O (1136 cm⁻¹) and C-O-SO₃ (1024 cm⁻¹), which are characteristic of fucoidan, were identified in the first polysaccharidic extract, whereas guluronic units (G) (1017 cm⁻¹) and mannuronic units (M) (872 and 812 cm⁻¹) confirmed the separation of alginate. The DNA binding studies of the isolated polysaccharides revealed an electrostatic and an intercalation interaction of DNA with fucoidan and alginate, respectively. Both antioxidant activity assays revealed improved antioxidant activity for both fucoidan and alginate compared to the standard α-tocopherol.