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The partial and the integral enthalpies of mixing of liquid ternary Al–Cr–Ni alloys have been determined by high temperature iso‐peribolic calorimetry at 1718–1731 K. Measurements for ternary alloys were performed along 4 isopleths with xCr:xNi of 0.20:0.80, 0.50:0.50, 0.70:0.30, and 0.85:0.15. The results were analytically described by the thermodynamically adapted power series according to the Kohler interpolation geometry as well as by the regular association model using the parameters for the constituent binaries and assuming that ternary association reactions with the stoichiometry Al2Cr1Ni1 take place in the liquid state. The results were also compared with the calculated ones using the database for the Al–Cr–Ni system. The Gibbs energy of mixing of liquid and undercooled liquid Al–Cr–Ni alloys were estimated in the whole composition range. The latter function demonstrates that the minimum (−41.5 kJ · mol−1) shows up near the ternary composition Al0.48Cr0.04Ni0.48.