The effects of Bi content as a trace element on the microstructure and the solidification path of A356.2 alloy have been investigated. The alloys containing different Bi levels (0, 20, and 200 ppm) have been modified by sodium. The experimental alloys have been thermally analyzed by using the two‐thermocouple method. Metallographic and image analysis techniques have been used to quantitatively examine the microstructural changes occurring at different Bi and Na concentrations. The results indicate how the presence of Bi as a trace element affects the eutectic structure. Upon increasing the Bi level, the nucleation and growth temperatures of eutectic Si raise, and the eutectic Si particles appear coarser in Na‐modified alloys. The EBSD analyses show that the crystallographic orientation between eutectic Al and surrounding primary Al dendrites becomes identical in Na‐modified Bi‐containing alloy. Furthermore, an irregular Bi + (Mg,Na)3Bi2 eutectic is formed prior to the precipitation of the eutectic Si, thus reducing the efficiency of Na addition to fully modify the eutectic Si.