Thermo-compression process—compression of pure cellulose under high temperatures and pressures—is a recent method to produce biodegradable materials. For such processes, experimental measurements and study of properties and behavior of cellulose are difficult to carry out. To overcome these difficulties, a complete pressure–volume–temperature investigation is needed as carried out in this work. To develop a predictive thermodynamic PVT model of cellulose theoretically, the modified Sanchez and Lacombe equation of state together with the implementation of the Hoftyzer and van Krevelen group contribution method and the Boudouris modification to the Constantinou and Gani’s group contribution method were coupled to the Compressible Regular Solution theory. The developed method is a pure predictive model and to examine the accuracy of theoretically calculated PVT data by the model, some available PVT data of cellulose at temperatures from 25 to 180 °C and pressures from 19.6 to 196 MPa (219 data points) were collected from literature. The comparisons were made and the agreement between the calculations and the experimental data were acceptable with a Cumulative Absolute Relative Deviation of 0.04 %. Consequently, the model can be used for prediction of thermodynamic properties of cellulose and cellulose-containing mixtures.