A large bulk nanostructured Ni65Al21Cr14alloy with dimensions of Φ 100 mm × 6 mm was produced by combustion synthesis technique followed with rapid solidification. The Ni65Al21Cr14alloy was composed of γ′-Ni3Al/γ-Ni(Al, Cr) eutectic matrix and γ-Ni(Al, Cr) dendrite. The eutectic matrix consisted of 80–150 nm cuboidal γ′-Ni3Al and 2–5 nm γ-Ni(Al, Cr) boundary. The dentrite was comprised of high-density growth twins with about 3–20 nm in width. The nanostructured Ni65Al21Cr14alloy exhibited simultaneously high fracture strength of 2200 MPa and good ductility of 26% in compression test.