The steroid hormones, cortisol and dehydroepiandrosterone (DHEA) are the two main peripheral secretory products of the hypothalamic-pituitary-adrenal stress-neuroendocrine axis. The diurnal pattern of cortisol secretory activity has been well characterised. Various aspects of this pattern have been related to time of awakening, light exposure, psychological dimensions of affect, immune function and systemic health and well-being. DHEA is also an important adrenocortical steroid whose secretory activity has been related to immune function, psychological and health variables. The most pronounced feature of the diurnal cortisol cycle is a burst of secretory activity following awakening with a diurnal decline thereafter. We mapped DHEA secretory activity onto this cycle by measuring both steroids in saliva samples collected at distinct time points over the diurnal cycle, synchronised to awakening. Both steroids, particularly DHEA, showed stability across days of sample collection. A main distinction between cortisol and DHEA was that although DHEA was elevated in post-awakening samples compared with later in the day there was no evidence of an awakening stimulatory burst of DHEA secretory activity. Although DHEA in many respects paralleled cortisol secretory activity there was some dissociation; mean levels were positively but not tightly correlated. The secretory pattern of DHEA is very stable whereas cortisol secretory activity seems more sensitive to day-to-day variability.