AbstractA new bio‐optical algorithm based on the green and red bands of the Medium Resolution Imaging Spectrometer (MERIS) is developed to differentiate the harmful algal blooms of Prorocentrum donghaiense Lu (P. donghaiense) from diatom blooms in the East China Sea (ECS). Specifically, a novel green‐red index (GRI), actually an indicator for a(510) of bloom waters, is retrieved from a semianalytical bio‐optical model based on the green and red bands of phytoplankton‐absorption and backscattering spectra. In addition, a MERIS‐based diatom index (DIMERIS) is derived by adjusting a Moderate Resolution Imaging Spectroradiometer (MODIS) diatom index algorithm to the MERIS bands. Finally, bloom types are effectively differentiated in the feature spaces of the green‐red index and DIMERIS. Compared with three previous MERIS‐based quasi‐analytical algorithm (QAA) algorithms and three existing classification methods, the proposed GRI and classification method have the best discrimination performance when using the MERIS data. Further validations of the algorithm by using several MERIS image series and near‐concurrent in situ observations indicate that our algorithm yields the best classification accuracy and thus can be used to reliably detect and classify P. donghaiense and diatom blooms in the ECS. This is the first time that the MERIS data have been used to identify bloom types in the ECS. Our algorithm can also be used for the successor of the MERIS, the Ocean and Land Color Instrument, which will aid the long‐term observation of species succession in the ECS.