The aim of this study is to develop a new EOS/G(ex)-type mixing rule with special attention to calculating the solid solubilities of aromatic hydrocarbons, aliphatic carboxylic acids, aromatic acids, and heavy aliphatic and aromatic alcohols in supercritical carbon dioxide. A volume correction term is applied with a combination of second and third virial coefficients which the equation for the third virial coefficient is quadratic, according to the suggestion by Hall and Iglesias-Silva. In this study, the cubic Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state have been used to calculate the solid solubilities of 23 solutes in supercritical CO2, by using six mixing rules. namely, the Wong-Sandier (WS) rule, the Orbey-Sandler (OS) rule, the van der Waals one fluid rule with one (VDW1) and two (VDW2) adjustable parameters, the covolume dependent (CVD) rule and the new mixing rule. in all cases, the NRTL model was chosen as the excess Gibbs free energy model. The coefficients of the NRTL model and the binary interaction parameters of six mixing rules with two EOSs (PR and SRK EOSs) have been determined for 100 data sets of 23 binary systems over a wide range of temperatures and pressures covering more than 970 experimental data points which are reported in the literature. The results show that the PR EOS with the new mixing rule model is more accurate than the PR and SRK EOSs with the other mixing rules for solid solubility calculations in supercritical carbon dioxide. The regressed interaction parameters of the binary system, without any further modification, were then extended to four ternary mixtures, giving satisfactory results of the solid solubilities in supercritical CO2. (C) 2009 Elsevier B.V. All rights reserved.