The invention provides a beryllium-free nickel-free high-ductility zirconium-base block body amorphous alloy and a preparation method thereof. The alloy comprises, by atom, 38-50% of Zr, 2-15% of Hf, 20-30% of Cu, 5-10% of Fe, 10-15% of Al, 0-5% of Co, 0-5% of Ag and 0-5% of Nb. The electric arc melting copper mould casting method is adopted for preparation. The amorphous alloy is free of metal elements such as Be and Ni, and biocompatibility of the zirconium-base alloy is improved. The high amorphous forming capacity is achieved, and the zirconium-base block body amorphous alloy with the critical size being no less than 5 mm can be prepared through the copper mould casting method. According to the beryllium-free nickel-free high-ductility zirconium-base block body amorphous alloy, high hardness is achieved, and vickers hardness is larger than 540 Hv; the plastic deformation capacity being larger than 3% is achieved; and the super-cooled liquid phase region range is wide and reaches 92 K at most. The beryllium-free nickel-free high-ductility zirconium-base block body amorphous alloy and the preparation method thereof has very wide application prospects in the fields of biomedical materials such as a precise complex medical component, a joint prosthesis and a human skeleton.