The invention discloses a germanium-containing nickel-free non-phosphorus large-sized palladium-based amorphous alloy and a preparation method thereof. The alloy comprises, in atomic percent, 73-80% of Pd, 0-8% of Cu, 0-18% of Si, 2-20% of Ge and 0-6% of Ag. The alloy mainly has the advantages that the alloy is free from nickel and phosphorus, potential biological toxicity is greatly reduced, biological compatibility is improved, the smelting preparation method is simple and convenient, the alloy has strong amorphous forming ability, a glass-coated medium process is used for purification, water quenching and rapid cooling, the palladium-based amorphous alloy with the critical size of 1-8mm can be prepared, components with the strongest glass formation ability can be prepared into the amorphous alloy with the critical size not smaller than 4mm by an electric arc melting copper mold suction-casting method, the amorphous alloy with the critical size not smaller than 8mm can be prepared bya preparation mode 3, and the alloy has plastic deformation capacity higher than 3% and has a 40-60K super-cooled liquid region.