In the present work, the influence of Ca2+ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca2+ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)2 precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the "free ion activity model" (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca2+-LAS-) and not due to the precipitated molecule, Ca(LAS)2. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca2+/Mg2+ ions, according to the results presented in this work.