We report the isotope fractionation of zinc (Zn) associated with a redox reaction between Zn(0) and Zn(II). Zn isotopes were found fractionated in pyrometallurgical biphase extraction between liquid zinc and molten chloride. The isotopic composition of Zn in the molten chloride phase was analyzed by multiple collector inductively coupled plasma mass spectrometry and reported as (m)Zn/64Zn (m = 66, 67, and 68) ratios. The observed isotope fractionation consists of the mass-dependent and mass-independent isotope effects. The contributions of the nuclear mass and the nuclear volume to the overall isotope effect were evaluated by employing first-principles quantum calculations and using reported isotope shifts in atomic spectra. The magnitude of the mass-dependent isotope effect was explained by the sum of the isotope effect via intramolecular vibrations and the correction to the Born-Oppenheimer electronic energy. The mass-independent isotope effect was correlated with the Gibbs free energy change in the redox reaction.