Under climate change scenarios, the contribution of macroalgae to carbon sequestration has attracted wide attention. As primary producers, macroalgae can release substantial amounts of dissolved organic carbon (DOC) in seawater. However, little is known about the molecular composition and chemical properties of DOC derived from macroalgae and which of them are recalcitrant DOC (RDOC) that can be sequestered for a long time in the ocean. In the most intensive seaweed (kelp) farming area (Sanggou Bay) in China, we found that kelp mariculture not only significantly increased DOC concentration, but also introduced a variety of new DOC molecular species, many of which were sulfur-containing molecules. A long-term DOC degradation experiment revealed that those DOC with strong resistance to microbial degradation, i.e., RDOC, account for approximately 58% of the DOC extracted from kelp mariculture area. About 85% (3587 out of 4224 with different chemical features) of the RDOC molecular species were steadily present throughout the long-term degradation process. 15% (637 out of 4224 with different chemical features) of the RDOC molecular species were likely newly generated by microorganisms after metabolizing macroalgae-derived labile DOC. All these stable RDOC should be included in the blue carbon budgets of seaweed.