Novel casting alloys that retain their mechanical strength at temperatures up to 300 °C are needed in order to improve automotive engine efficiency. The addition of Zr and V is a promising combination as a means of introducing the thermally stable cubic Al3ZrxV1-x nano-precipitates. In this project, the evolution of the Al3ZrxV1-x precipitates in multi-component cast aluminium alloys was characterised in a statistically significant way using small-angle X-ray scattering (SAXS). Unlike established metallurgical techniques, such as transmission electron microscopy (TEM), SAXS measures billions of precipitates in a single experiment.Two Al-6.8Si (wt.%) alloys were employed. One contained 0.30 wt.% Zr and 0.30 wt.% V and the other 0.37 wt.% Zr and 0.34 wt.% V. The alloys were cast and isothermally aged at 400 °C for times ranging from 3 to 50 h. Synchrotron SAXS was undertaken at the Diamond Light Source (DLS). Direct evaluation methods of SAXS spectrum were employed in order to extract information about the average precipitate size, precipitate size distribution and their evolution with ageing time. These results were compared with the results provided via TEM, both validating the methodology, and demonstrating the benefits and drawbacks of SAXS.From the SAXS analysis, the Guinier radius, Rg, was found to increase with ageing time from around 2 nm at 3 h to approximately 9 nm at 50 h. Precipitate volume fraction also increased from 0.11 vol.% to 0.24 vol.% for the lower solute alloy and from 0.14 vol.% to 0.33 vol.% for the higher solute one. In both alloys, the precipitate number density was observed to continuously decrease with ageing time. For the higher solute alloy, the average precipitate radius from the TEM measurements was found to be consistently smaller than Rg.Such a study is important because it extends the experimental SAXS methodology previously used only in simplified alloys to multi-component cast alloys of industrial importance. Moreover, the findings from this investigation suggest that both alloys quickly enter a stage where the precipitate growth and coarsening overlap, and the precipitate number density continuously decreases with time. Finally, this study underlines the importance of preliminary SAXS data treatment and provides an analytical guide in order to successfully characterize low volume fraction of precipitates in multi-component cast alloys.