Data from three cruises conducted in the northern South China Sea (SCS),the Daya Bay and the Pearl River Estuary,respectively,were examined to access the variations of phytoplankton size structure. A spectral mixing model was established to retrieve phytoplankton size parameter from phytoplankton absorption spectra,with Sf as a proxy of the size parameter. There were significant similarities in phytoplankton size structure in the estuarine and coastal waters; however,it is very dif-ferent in the open ocean. In the estuarine and coastal waters,the micro-phytoplankton plays a dominant role,while in the open ocean the pico-phytoplankton was the dominant species. Phytoplankton size parameter tended to decrease with increasing micro-phytoplankton,and to increase with increasing pico-phytoplankton. There was an increasing trend for chlorophyll a concentration from the open ocean to the coastal sea. Phytoplankton size parameter showed a power function relation with chlorophyll a concentration and decreased with increasing chlorophyll a concentration. The results showed that there was a relationship between phytoplankton size parameter retrieved from the spectral mixing model and the bio-optical characteristics in different circumstances of the SCS. This spectral mixing model provided a simple tool for extracting ecological information of phytoplankton species from optical measurements,and can be used to analyze the influence of dominant phytoplankton size structure on optical characteristics.