The effects of adding 0.02 or 0.06at.% Si to Al–0.06Sc–0.06Zr (at.%) are studied to determine the impact of Si on accelerating Al3(Sc,Zr) precipitation kinetics in dilute Al–Sc-based alloys. Precipitation in the 0.06at.% Si alloy, measured by microhardness and atom-probe tomography (APT), is accelerated for aging times <4h at 275 and 300°C, compared with the 0.02at.% Si alloy. Experimental partial radial distribution functions of the α-Al matrix of the high-Si alloy reveal considerable Si–Sc clustering, which is attributed to attractive Si–Sc binding energies at the first and second nearest-neighbor distances, as confirmed by first-principles calculations. Calculations also indicate that Si–Sc binding decreases both the vacancy formation energy near Sc and the Sc migration energy in Al. APT further demonstrates that Si partitions preferentially to the Sc-enriched core rather than the Zr-enriched shell in the core/shell Al3(Sc,Zr) (L12) precipitates in the high-Si alloy subjected to double aging (8h/300°C for Sc precipitation and 32days/400°C for Zr precipitation). Calculations of the driving force for Si partitioning confirm that: (i) Si partitions preferentially to the Al3(Sc,Zr) (L12) precipitates, occupying the Al sublattice site; (ii) Si increases the driving force for the precipitation of Al3Sc; and (iii) Si partitions preferentially to Al3Sc (L12) rather than Al3Zr (L12).