Diatom and water chemistry samples were collected from 49 lakes, pools and rivers on Byers Peninsula (Livingston Island, South Shetland Islands) during the summer of 2009. A diverse diatom flora of 143 taxa was found. Fragilaria capucina s.l., Psammothidium papilio, Navicula dobrinatemniskovae and several Nitzschia taxa dominated the flora. The biogeographical analysis showed that more than 55% of all observed taxa presented a restricted Antarctic biogeographic distribution and only 30% had a cosmopolitan distribution, contrary to previously published data. Cluster analysis and Principal Components Analysis were used to classify the samples based on their chemical characteristics, revealing that nutrients and specific conductance were the main factors dividing the samples into four groups: young lakes, coastal lakes, larger lakes on the central plateau and smaller, temporary pools. Diatom communities corresponded well to this division and were strongly influenced by salinity and nutrients.