Green organic entrainers and natural deep eutectic solvents (NADESs) possessing high boiling points and decomposition temperatures, exhibit considerable potential as advanced materials for green entrainers in extractive distillation. However, there is a wide range of solvents to choose from and their properties are only rarely available for use in process design and simulation. The present study aims to assess the selection parameters and examine the performance of and select green organic entrainers and NADESs for the separation of the close boiling mixture methylcyclohexane-toluene. The evaluation carried out was based on selectivity and relative volatility values obtained by using predictive models. COSMO-RS (a unimolecular quantum chemical calculation) was employed to predict the selectivity at infinite dilution, while group contribution methods such as UNIFAC and modified UNIFAC (Dortmund) were used to predict the relative volatility. According to the calculated results, the selectivity appeared a more important selection parameter than the performance index. The relative volatility prediction using the UNIFAC and UNIFAC Dortmund methods exhibits comparable trends to the selectivity results derived from COSMO-RS. However, the use of UNIFAC and modified UNIFAC (Dortmund) in predicting the relative volatility of NADES containing mixtures is limited due to the absence of functional group parameters. This CAPE study reveals that, based on the calculated selectivity (using COSMO-RS) and relative volatility (using UNIFAC, and modified UNIFAC (Dortmund)), most of the proposed green organic entrainers and NADESs exhibit a higher or comparable selectivity and relative volatility as the benchmark entrainers. This confirms the potential of the evaluated green entrainers with higher selectivity and relative volatility to enhance the design of extractive distillation. Therefore, the cost, energy and water consumption, as well as CO2 emissions in the methylcyclohexane and toluene separation can be reduced.@en