The solubility of ε-CL-20 in 12 eco-friendly biobased solvents was measured using the static method in the temperature range from 283.15 to 323.15 K (0.1 MPa). Under given temperature conditions, the solubility order of ε-CL-20 is ethyl lactate > isoamyl acetate > methyl lactate > butyl lactate > diethyl carbonate >2-methyl tetrahydrofuran > propanediol butyl ether > ethylene glycol > propylene glycol > 4-methyl-2-pentanol > cyclopentyl methyl ether > anisole. The modified Apelblat equation and Van't Hoff model were utilized to correlate the solubility data, and solvent effects were investigated using the Kamlet−Taft linear solvation energy relationship model. In addition, the interaction between solute and solvent molecules was further studied by molecular simulation. The thermodynamic properties of ε-CL-20 in new green solvents reported in this study provide significant support for green industrial production, sustainable development, and further theoretical research of ε-CL-20.