A 38-year-old man was found dead in bed dressed in female clothing with a mouth gag, handcuffs and bindings around the genitals and limbs. A respirator was also covering the mouth and nose. There were no suspicious circumstances and a diagnosis of death due to sexual asphyxia was made. Following the subsequent discovery of bottles of chloroform in the bedroom, head space analysis of blood confirmed the presence of chloroform, with a blood level of 33 mg/L. Death was, therefore, attributed to a combination of chloroform toxicity and upper-airway obstruction. Headspace analysis with follow-up quantitation may, therefore, be a useful adjunct to the investigation of such cases when devices such as respirators or gas masks are found with the body.