Effect of refining element phosphorus (P) on the morphology of the primary silicon in the Al–70 wt.%Si alloy was investigated via the electromagnetic levitation (EML) technique. The morphology and microstructure were analyzed by using high-speed video (HSV) and scanning electron microscopy (SEM). It was found that the morphology of primary silicon transformed from dendrites with several branches to blocky shape, and then to equiaxed grains in Al–70 wt.%Si and Al–70 wt.%Si–1.0 wt.%P alloys with increasing of undercooling. The nucleation number and nucleation rate increased exponentially with the increase of undercooling for both alloys. Finally, the growth velocity of primary silicon was discussed in combination with classical theory.