The microstructure characteristics of the spray-formed and melt-spun Al85Nd5Ni10 and Al89La6Ni5 alloys were studied. The spray forming process was demonstrated to produce a bulk scale hybrid composite consisting of amorphous and nanostructured phases directly without the need of an amorphous precursor. The spray-formed Al89La6Ni5 deposit (~1 mm in thickness) were partially amorphous, and the amorphous phase came from the undercooled liquid droplets upon deposition. The as-spray-formed Al85Nd5Ni10 deposit (~20 mm in thickness) was completely crystallized due to the devitrification of the retained amorphous phase to nano-scale secondary crystals upon deposition. Primary crystals (~1 μm) are dispersed uniformly in the bulk spray-formed amorphous/or partial amorphous composites and many distinctive deformation twins also are observed in the crystals, however, not twins found in the corresponding completely devitrified ribbon. This is mainly because of the stirring and impacting force offered by high velocity droplets during spray forming and the mismatch of thermal expansion coefficient between primary crystals and adjacent amorphous matrix.