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A eutectic point in Pr-rich Pr-(Cu,Ni)-Al alloys was experimentally determined by measuring the solidus temperature (T m ) and liquidus temperature (T l ). It was found that Pr 68 (Cu 0.5 Ni 0.5 ) 25 Al 7 (at.%) is at the eutectic composition in the pseudoternary Pr-(Cu 0.5 Ni 0.5 )-Al alloys. The alloy Pr 68 (Cu 0.5 Ni 0.5 ) 25 Al 7 exhibits better glass-forming ability (GFA) than the ternary eutectic alloy Pr 68 Cu 25 Al 7 . However, the best GFA was obtained at an off-eutectic composition (Pr 54 [Cu 0.5 Ni 0.5 ] 30 Al 16 ) in the Pr-(Cu 0.5 Ni 0.5 )-Al alloys, which can be formed in fully amorphous rods with diameter of 1.5 mm by copper mold casting. Moreover, the glass-transition temperature T g increases quickly (from 367 to 522 K) with the increasing of the Al content (from 3 to 27 at.%). The deviation of the best GFA composition from the eutectic point [Pr 68 (Cu 0.5 Ni 0.5 ) 25 Al 7 ] was explained in terms of the asymmetric coupled eutectic zone, the competition between growth of crystalline phase and formation of amorphous, and the higher glass-transition temperature T g on the hypereutectic side.