The interaction between vacancies and Sn and Cu solute atoms in an Al-1.7at.%Cu- 0.01at.%Sn alloy was investigated by exploring the effect of incorporating natural ageing into conventional age hardening treatment. It was found that provided the artificial ageing temperature does not exceed a critical value between 160°C and 200°C, a narrow window of natural ageing (3-100 h) will result in a significant acceleration of the age hardening response and no decrease in peak hardness. Transmission electron microscopy showed that this effect reflects a large and rapid increase in number density of Cu GP(I) zones, and, to a lesser extent, of θ". The distribution and number density of θ' are essentially unaffected. Three-dimensional atom probe provided strong evidence that refinement of GP(I) zone distribution is not due to clustering of Cu atoms onto pre-existing Sn clusters. Instead it appears to be caused by a subtle interaction between vacancies, Sn and Cu atoms.