The rate at which carbon monoxide displaces oxygen from its combination with haemoglobin in solution, has been measured spectrophotometrically, using a rapid-mixing stopped-flow technique. 2. In the presence of carbon dioxide, the reaction proceeds by a unimolecular dissociation, with a rate constant r. 3. The relationship of the reciprocal of r to the ratio PO2/PCO is non-linear, and a different curve is obtained at each carbon monoxide concentration. 4. From measurements of the rate constant at temperatures between 5 and 35 degrees C, it is concluded that the non-linearity is due to the formation at a finite rate of an intermediate complex, CO2Hb4O6, by the reaction of carbon dioxide with Hb4O6.