Asphalt bitumens are complex colloidal systems of high viscosity and complex behavior, which are mainly used for making asphalt concrete for road surfaces. Thermal and rheological characterizations are needed to understand their complex behavior, particularly at the processing stage. Prediction of properties at short and long observation times is usually performed through time-temperature superposition (TTS) models, which make use of some calculated shift factors. The influence of crystallization-like transformation processes on the validity of these shift factors is investigated here by temperature-modulated differential scanning calorimetry (TMDSC). Four asphalt emulsions are considered in this work, each one with a specific transformation behavior. The structure-properties relationships are explained on the basis of the transformation profiles and rheological data.