Titration of haem with pyridine in alkaline media of low ionic strength yields a true pyridine haemochromogen, compound III, at very low concentrations of pyridine. 2. Graphical analysis of this titration gives the first spectrophotometric evidence for a dimeric haem. 3. Compound III is unstable and tends to aggregate to a second compound, compound II, whose formation is enhanced under those conditions favourable to hydrophobic bonding. 4. At higher concentrations of pyridine, compound II is dispersed to yield the classical pyridine haemochromogen, compound I, whose spectral properties are essentially those of pyridine haemochromogen in a non-aqueous medium.