The process of ultrathin Al-induced crystallization of amorphous Si (a-Si) has been investigated by using high-resolution transmission electron microscopy and Auger electron spectroscopic depth profiling. Ultrathin Al overlayers, with thicknesses of 2.0 and 4.5 nm, have been shown to be capable of inducing full crystallization of an a-Si bottom layer as thick as 40 nm at temperatures as low as 320 °C. After full crystallization of a-Si, the Al of the original 2.0-nm Al overlayer completely moved through the Si layer, leaving a high-purity, large-grained crystalline Si layer above it. Such movement of Al also occurs for the originally 4.5-nm Al overlayer, but in this case the crystallized Si layer is relatively fine-grained and contains ∼5.0 at.% of residual Al nanocrystals distributed throughout the layer. The observations have been interpreted on the basis of sites available for nucleation of crystalline Si in the microstructure of the Al/Si layer system upon annealing.