A complete understanding of the processes underlying the transformation of sapwood into heartwood requires consideration of the chemical as well as other aspects of the change. A review of recent investigations into chemical topics is presented. There is a decrease in the storage materials from the outer and middle sapwood to the heartwood boundary, although there is one case where the reverse trend of sugar content was found and this may be a seasonal effect. The evidence presented shows that, in some species, some metabolic pathways operating at the sapwood-heartwood boundary differ from those in the sapwood. It is not known whether the reactions operating at the heartwood boundary include those previously operating in the sapwood or whether the new compounds are added to those already present. The composition of the heartwood extractives in a species is the same in different samles. Examples are given to show that the affected wood resulting from different forms of damage can be chemically different from normal heartwood. Consequently, the processes leading up to the death of the living cells can have a great influence on the composition of the extractives. Accordingly it is not only the constant composition of normal heartwood extractives that is under genetic control, but also the processes which initiate their formation. The intermediate zone and the factors which could initiate heartwood formation and control the amount of extractives formed, are considered. Evidence shows the extractives to be formed at the heartwood periphery from translocated carbohydrate, the amount of which is possibly under the control of growth-promoting hormones.