Abstract This study reports data on arsenic speciation in two green algae species (Cladophora sp. and Chara sp.) and in five aquatic plants (Azolla sp., Myriophyllum aquaticum, Phylloscirpus cf. desserticola, Potamogeton pectinatus, Ruppia filifolia and Zannichellia palustris) from the Loa River Basin in the Atacama Desert (northern Chile). Arsenic content was measured by Mass spectrometry coupled with Inductively Coupled Plasma (ICP–MS), after acidic digestion. Liquid chromatography coupled to ICP–MS was used for arsenic speciation, using both anionic and cationic chromatographic exchange systems. Inorganic arsenic compounds were the main arsenic species measured in all samples. The main arsenic species in the extracts of freshwater algae and plants were arsenite and arsenate, whereas glycerol-arsenosugar (gly-sug), dimethylarsinic acid (DMA) and methylarsonic acid (MA) were present only as minor constituents. Of the samples studied, algae species accumulated more arsenic than aquatic plants. Total arsenic content ranged from 182 to 11100 and from 20 to 248mgAskg−1 (d.w.) in algae and freshwater plants, respectively. In comparison with As concentration in water samples, there was hyper-accumulation (>0.1% d.w.) in Cladophora sp.