The shape of the temperature vs. specific entropy diagram of a working fluid is very important to understanding the behavior of fluid during the expansion phase of the organic Rankine cycle or similar processes. Traditional wet-dry-isentropic classifications of these materials are not sufficient; several materials remain unclassified or misclassified, while materials listed in the same class might show crucial differences. A novel classification, based on the characteristic points of the T–s diagrams was introduced recently, listing eight different classes. In this paper, we present a map of these classes for a model material, namely, the van der Waals fluid in reduced temperature (i.e., reduced molecular degree of freedom) space; the latter quantity is related to the molar isochoric specific heat. Although van der Waals fluid cannot be used to predict material properties quantitatively, the model gives a very good and proper qualitative description. Using this map, some peculiarities related to T–s diagrams of working fluids can be understood.