Hardness measurements and 3-dimensional atom probe analysis have been used to characterise the precipitation behaviour in two 6xxx series aluminium alloys, one Cu-free alloy (Al-0.78at%Mg- 0.68at%Si) and one Cu-containing alloy (Al-0.78at%Mg-0.68at%Si-0.30at%Cu). The heat treatments consisted of either natural ageing or pre-ageing at 353K followed by a paint-bake treatment at 453K. Natural ageing was seen to increase the hardness, and hence reduce formability compared to pre-ageing. In addition, the strengthening effect of artificial ageing was less after natural ageing than after pre-ageing. In the Cu-free alloy, needle-like β″ was observed to form only after a pre-ageing treatment during the first 60 minutes of a paint-bake treatment. In the Cucontaining alloy, needle-like β″ formed during paint bake in both the naturally-aged and pre-aged material, although it is formed more rapidly after pre-ageing. This was accompanied by an increase in strength over the Cu-free alloy and indicates that Cu reduces the deleterious effect of natural ageing.