Soil arsenic (As) pollution is still a major concern due to its high toxicity and carcinogenicity, thus, the study of decontamination techniques, as the organic amendment applications, keeps upgrading. This research evaluates the potential remediation of peat in different As-polluted soils, by assessing the decrease of As solubility and its toxicity through bioassays. Obtained reduction in As solubility by peat addition was strongly related to the increase of humic substances, providing colloids that allow the complexation of As compounds. Calcareous soils have been the least effective at buffering As pollution, with higher As concentrations and worse biological response (lower soil respiration and inhibition of lettuce germination). Non-calcareous soils showed lower As concentrations due to the higher iron content, which promotes As fixation. Although in both cases, peat addition improves the biological response, it also showed negative effects, hypothetically due to peat containing toxic polyphenolic compounds, which in the presence of carbonates appears to be concealed. Both peat dose tested (2% and 5%) decreased drastically As mobility; however, for calcareous soils, as there is no phytotoxic effect, the 5% dose is the most recommended; while for non-calcareous soils the efficient peat dose for As decontamination could be lower.