The Caprivi basin in Namibia has been affected by severe flooding in recent years resulting in deaths, displacements and destruction of infrastructure. The negative consequences of these floods have emphasized the need for timely, accurate and objective information about the extent and location of affected areas. Due to the high temporal variability of flood events, Earth Observation (EO) data at high revisit frequency is preferred for accurate flood monitoring. Currently, EO data has either high temporal or coarse spatial resolution. Accurate methodologies for the estimation and monitoring of flooding extent using coarse spatial resolution optical image data are needed in order to capture spatial details in heterogeneous areas such as Caprivi. The objective of this work was the retrieval of the fractional abundance of water (γ w ) by applying a new spectral indices-based unmixing algorithm to Medium Resolution Imaging Spectrometer Full Resolution (MERIS FR) data using a minimum number of spectral bands. These images are technically similar to the OLCI image data acquired by the Sentinel-3 satellite, which are to be systematically provided in the near future. The normalized difference wetness index (NDWI) was applied to delineate the water surface and combined with normalized difference vegetation index (NDVI) to account for emergent vegetation within the water bodies. The challenge to map flooded areas by applying spectral unmixing is the estimation of spectral endmembers, i.e., pure spectra of land cover features. In our study, we developed and applied a new unmixing method based on the use of an ensemble of spectral endmembers to capture and take into account spectral variability within each endmember. In our case study, forty realizations of the spectral endmembers gave a stable frequency distribution of γ w . Quality of the flood map derived from the Envisat MERIS (MERIS) data was assessed against high (30 m) spatial resolution Landsat Thematic Mapper (TM) images on two different dates (17 April 2008 and 22 May 2009) during which floods occurred. The findings show that both the spatial and the frequency distribution of the γ w extracted from the MERIS data were in good agreement with the high-resolution TM retrievals. The use of conventional linear unmixing, instead, applied using the entire available spectra for each image, resulted in relatively large differences between TM and MERIS retrievals.