Pyrrolizidine alkaloids (PA)s are natural toxins produced by a variety of plants including ragwort. The PAs present a serious health risk to human and livestock. Although these compounds have been extensively studied in food and feed, little is known regarding their environmental fate. To fill this data gap, we investigated the occurrence of PAs in ragwort plants, soils and surface waters at three locations where ragwort was the dominant plant species to better understand their environmental distribution. The concentrations of PAs were quantified during the full growing season (April–November) and assessed in relation to rain events. PA concentrations ranged from 3.2–6.6 g/kg dry weight (dw) in plants, 0.8–4.0 mg/kg dw in soils, and 6.0–529 μg/L in surface waters. Maximum PA concentrations in the soil (4 mg/kg) and water (529 μg/L) were in mid-May just before flowering. The average distribution of PAs in water was approximately 5 g/10,000 L, compared to the average amounts present in ragwort (506 kg/ha), and soil (1.7 kg/ha). In general, concentrations of PAs increase in the soil and surface water following rain events.