The precipitation of biphenyl from twenty organic solvents using carbon dioxide as antisolvent was examined in this study. The experimental results showed that even though a large volume expansion of some solvents after the addition of the compressed CO2, biphenyl could not be precipitated due to that CO2 acted as a cosolvent rather than an antisolvent in these operations. The criterion for the precipitation of biphenyl from a solvent was proposed as that the solubility parameter of the solvent should be larger than 17.4 MPa1/2 but smaller than that of biphenyl (21.6 MPa1/2). When the solubility parameter of a solvent was closer to that of biphenyl, more biphenyl was precipitated. For a solvent not causing the precipitation of biphenyl, the proposed criteria can be applied to determine what the other solvent and the minimum amount should be added into the solvent to result in a precipitation.