Segregation can seriously damage the mechanical properties of the aluminum alloys. 6061 aluminum alloy wheel spokes were prepared by squeeze casting. To investigate the formation mechanism of segregation, the microstructure of the alloy was observed using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction and electron microprobe analysis methods. The Gibbs energy of each phase during solidification was calculated by JMatPro. Results show that the segregation phases in the R-joint of the wheel spokes are mainly composed of Mg2Si, β-AlFeSi and Al5Cu2Mg8Si6 intermetallics. During the solidification of the 6061 aluminum alloy wheels, Mg2Si and α-AlFeSi phases precipitate in the mushy zone at first. With the decrease of temperature, α-AlFeSi transforms into β-AlFeSi, while Al5Cu2Mg8Si6 precipitates from the solid-state aluminum alloy after solidification. Segregation at the R-joint of wheel spokes is mainly caused by insufficient cooling, so the cooling during alloy solidification should be enhanced to avoid segregation.