It is a challenge to degrade sulfated polysaccharides without stripping sulfate groups. In the present study, a photocatalytic method was applied to degrade fucoidan, a sulfated polysaccharide from brown algae. The degradation with varying addition amounts of H₂O₂ and TiO₂ were monitored by high performance gel permeation chromatography (HPGPC) and thin layer chromatography (TLC), and fucoidan was efficiently degraded with 5% TiO₂ and 0.95% H₂O₂. A comparison of the chemical compositions of 2 products obtained after 0.5 h and 3 h illumination, DF-0.5 (average Mw 90 kDa) and DF-3 (average Mw 3 kDa), respectively, with those of fucoidan indicates the photocatalytic degradation did not strip the sulfate groups, but reduced the galactose/fucose ratio. Moreover, 12 oligosaccharides in DF-3 were identified by HPLC-ESI-MSⁿ and 10 of them were sulfated. In addition, DF-0.5 showed anticoagulant activity as strong as fucoidan while DF-3 could specifically prolong the activated partial thromboplastin time. All samples exerted inhibition effects on the intrinsic pathway FXII in a dose-dependent manner. Thus, photocatalytic degradation demonstrated the potential to prepare sulfated low-molecular-weight fucoidan with anticoagulant activity.