Marine dissolved organic matter (DOM) constitutes a major carbon pool in the global carbon cycle. Characterization of its chemical composition will improve our understanding of its role in global biogeochemical cycles. Currently, solid phase extraction (SPE) followed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis has become a powerful approach to characterize the molecular composition of DOM. However, some components in marine DOM, such as highly oxygenated tannin-like molecules, were lost during the SPE process. In this study, a sequential combination of co-precipitation and SPE procedure was proposed to improve the yield of marine DOM extraction. Ferric hydroxide was used as the co-precipitation agent to separate marine DOM, and SPE was carried out for the extraction of DOM from dissolved and precipitate fractions. The total yield in total organic carbon (TOC) and the number of assigned molecules of SPE-DOM increased by 25% and 51%, respectively, compared with those by direct SPE process. The combined process has good selectivity on tannin-like compounds. The result is instructive for the understanding of DOM molecular composition and potential for a routine method for DOM extraction from environmental water samples, especially for marine DOM containing a small amount of tannin-like compounds.