AbstractChlorpyrifos [O,O‐diethyl O‐(3,5,6‐trichloro‐2‐pyridyl) phosphorothioate] is an organophosphorus insecticide applied to soil to control pests both in agricultural and in urban developments. Typical agricultural soil applications (0.56 to 5.6 kg ha−1) result in initial soil surface residues of 0.3 to 32 μg g−1. In contrast, termiticidal soil barrier treatments, a common urban use pattern, often result in initial soil residues of 1000 μg g−1 or greater. The purpose of the present investigation was to understand better the degradation of chlorpyrifos in soil at termiticidal application rates and factors affecting its behaviour. Therefore, studies with [14C]chlorpyrifos were conducted under a variety of conditions in the laboratory. Initially, the degradation of chlorpyrifos at 1000 μg g−1 initial concentration was examined in five different soils from termite‐infested regions (Arizona, Florida, Hawaii, Texas) under standard conditions (25°C, field moisture capacity, darkness). Degradation half‐lives in these soils ranged from 175 to 1576 days. The major metabolite formed in chlorpyrifos‐treated soils was 3,5,6‐trichloro‐2‐pyrid‐inol, which represented up to 61% of applied radiocarbon after 13 months of incubation. Minor quantities of [14C]carbon dioxide (< 5%) and soil‐bound residues (⩽ 12%) were also present at that time. Subsequently, a factorial experiment examining chlorpyrifos degradation as affected by initial concentration (10, 100, 1000 μg g−1), soil moisture (field moisture capacity, 1.5 MPa, air dry), and temperature 15, 25, 35°C) was conducted in the two soils which had displayed the most (Texas) and least (Florida) rapid rates of degradation. Chlorpyrifos degradation was significantly retarded at the 1000 μg g−1 rate as compared to the 10 μg g−1 rate. Temperature also had a dramatic effect on degradation rate, which approximately doubled with each 10°C increase in temperature. Results suggest that the extended (3–24 + years) termiticidal efficacy of chlorpyrifos observed in the field may be due both to the high initial concentrations employed (termite LC 50 = 0.2– 2 μg g−1) and the extended persistence which results from employment of these rates. The study also highlights the importance of investigating the behaviour of a pesticide under the diversity of agricultural and urban use scenarios in which it is employed.