Sulfated polysaccharide (SPS) derived from marine algae represents a promising renewable carbon biomass source. Through pyrolysis, SPS can be converted into C5 platform chemicals, including furfural (FF) and 5-methylfurura (5-MF). Understanding the fundamental reaction mechanisms during pyrolysis is essential for the advancing pyrolysis techniques. This work presents a detailed reaction mechanism that reveal new pathways leading to the most important products and intermediates. Simulations focusing on the initial steps in SPS pyrolysis showed that the unimolecular degradation of SPS is dominated by SO3 elimination, with a barrier height of 157.2 kJ/mol; ring-opening and glycosidic bond fission were identified as important competitive reactions, both of which have a barrier height of 207.6 kJ/mol and 260.1 kJ/mol, respectively. The 4,5-unsaturated acyclic rhamnose derived from the glycosidic bond fission of acyclic reducing end group can transform into 5-MF with high selectivity. In addition, the acyclic reducing end group is readily dehydrated to form a 2,3-unsaturated acyclic reducing end group, a reactive unsaturated intermediate. Its decomposition involves an 8-membered ring transition state that requires a low barrier height and results in the formation of a C5 fragment, which can be cyclized directly and dehydrated to form 5-MF. The majority of CO2 is mostly formed by the synergistic breakage of C-Ccarboxyl bonds and glycosidic bonds, with a barrier height of 197.9 kJ/mol. Moreover, a mechanism is uncovered for the formation of formic acid (FA) from a 4,5-unsaturated no-reducing end group. The major pyrolysis channel is initiated by a retro Diels-Alder reaction and followed by a retro-ene reaction to produce a 3,4-unsaturated non-reducing end group, which further decomposes into FA and a new 4,5-unsaturated non-reducing end group.