Lifetime prediction of polymer–polymer contacts is a major challenge. Current design methods stemming from metal contact surfaces lack accuracy because polymers behave differently, especially regarding temperature variations. Experiments were performed on a pin-on-disk setup alternating static and rotating elements. Common unfilled engineering polymers, viz. polyoxymethylene (POM), polypropylene (PP), polyamide 6.6 (PA6.6), and polycarbonate (PC) were tested at ambient and elevated temperatures. Material combinations were analyzed regarding the effects of load, velocity, temperature, and the product of contact pressure and sliding velocity (PV limit). The experimental results show that the PV limit is not predictive for polymer–polymer contacts; rather, each material combination has a critical factor that determines the wear and frictional values and thus the contact’s durability and lifetime. The critical factor is the value of contact pressure or sliding velocity or temperature at which there is sudden increase in wear rate. The experimental results also demonstrate that the application temperature in operation has an important influence on the lifetime. A temperature increase can either be beneficial or have a negative impact depending on the material combination. Resulting from the extensive experimental analysis, a new design method, based on the principle of deformation energy, is proposed. The new model is different from existing models because it includes thermal properties of the materials in contact and it makes use of the Péclet number. Because the proposed model requires only data sheet values and design parameters to predict wear volume, the model improves the support of engineers in designing durable polymer–polymer sliding contacts.