During age-hardening of certain Al-Zn-Mg-Cu alloys, a 90% hardness increase can occur with 75 seconds. The clustering and precipitation of solute element species during this early rapid hardening (RH) period has been investigated through atom probe tomography, transmission electron microscopy, and Vickers hardness measurements. This study has focussed on the effect of copper by analysing three alloys; Al-2.0Zn-1.8Mg-0.7Cu, Al-2.0Zn-1.7Mg-0.2Cu and Al-1.9Zn-1.7Mg (at.%). The early RH reaction in these alloys accounts for up to 70% of the total hardening (peak hardness minus as-quenched hardness) and takes place during the first 60 seconds of ageing. We report preferred solute-solute interactions in the as-quenched materials. This quenched-in nanostructure acts as a template for subsequent solute clustering, the nature of which we have correlated with ageing.