The presence of curium nuclides in irradiated nuclear fuel is well known, as is their occurrence in environmental materials exposed to liquid waste discharges from reprocessing plants and to fallout following the Chernobyl accident. Knowledge of the 242 Cm/244 Cm and 243 Cm/244 Cm atom ratios can be a useful tool for characterizing a source-term and assessing the burn-up history of nuclear fuel. Here, a practical technique, based on high-resolution alpha spectrometry and spectral deconvolution, is described by which the 243, 244 Cm multiplet can be resolved at the low activities typical of most environmental samples. The resulting 243 Cm/244 Cm ratio is then used to correct for any interference by 243 Cm in the 242 Cm window. The technique has been applied to the determination of the 243 Cm/244 Cm ratio in samples of seabed sediment collected near the Sellafield outfall, riverine sediment sampled downstream of the Mayak reprocessing plant and soil and lichen from within the Chernobyl exclusion zone. Near Sellafield, the 243 Cm/244 Cm ratio was found to be < 2%, while near Mayak and Chernobyl it was considerably higher, being approximately 6-8%.