Isobaric vapor liquid equilibrium (VLE) data for 2-methyl-butan-1-ol + 3-methyl-butan-1-ol CuCl2, ZnCl2, and FeCl3 systems were measured, respectively, in a modified Rose recirculation still at 101.3 kPa. The VLE data of binary systems were correlated with the e-NRTL and NRTL models. The ternary systems were predicted with the e-NRTL, and NRTL models. The results showed that the VLE of the 2-methylbutan-1-ol 3-methyl-butan-1-ol system in the presence of three salts was obviously different from that of the salt-free system. All salts showed a notable salting-out effect and followed the salting-out effect order of ZnCl2 > FeCl3 > CuCl2. The salting-out effect significantly increases the relative volatility of 2-methyl-butan-1-ol.