The effect of Si additions on vacancy behavior following solution treatment and quenching was studied for an Al-Cu-Mg-Ag alloy system using positron annihilation lifetime spectroscopy (PALS). Both the initial positron lifetime and steady state positron lifetime increase as the Si concentration increases. This behavior is interpreted in terms of Si interacting with vacancies, leading to their retention in the alloy. The ability of PALS to monitor vacancy behavior after solution treatment should allow the improved prediction of phase transformation kinetics and hence the tailoring of ageing treatments.