ZrNiTiCu and ZrNiTiCuAl alloys were amorphized using either a melt-spinning or ball-milling process in a high-energy planetary mill. The elemental powders were initially blended to the desired composition (in at.%) of Zr, 65; Cu, 27.5; Al, 7.5 and of Ti, 25; Zr, 17; Cu, 29; Ni, 29, respectively. The composition of alloys was chosen to be the same as for the bulk amorphous ZrCuAl and easy glass-forming ZrNiTiCu alloys. An almost fully amorphous structure was obtained after 80 h of milling in the case of both compositions. Transmission electron microscopy studies of ball-milled powders revealed the presence of nano-crystallites [2-5 nm for ZrCuAl and smaller (1-3 nm) for the ZrTiNiCu alloy]. High-resolution transmission electron microscopy of melt-spun ZrNiTiCuAl ribbons provided evidence of the amorphous structure.