In this paper, the isolation of limonene from orange peel and its application as an environmentally acceptable expanded polystyrene foam solvent during the recovery process was carried out. The residual limonene during the recovery process was removed by the precipitation process with the non-solvent (methanol). The effect of precipitation on the structure and thermal properties of expanded polystyrene foam was studied using infrared spectroscopy and differential scanning calorimetry. Infrared spectroscopy was used to determine the influence of precipitation on the structure of the foamed polystyrene investigated. By comparing the obtained spectrographs, there was no significant difference between the wave numbers of the vibration strips of the invastigated samples. It was found that precipitation did not significantly affect the structure of the foamed polystyrene investigated. Using the differential scanning calorimetry, the characteristic glass transition temperature of the investigated samples was determined. It was found that the precipitation process had a significant effect on the temperature of glass transition (Tg) of the expanded polystyrene foam, which proves that precipitation in this case is not a good method for removing limonene from recovered expanded polystyrene foam.