This review aims to explore the state of the knowledge and the state-of-the-art regarding bitumen rejuvenation. In particular, attention was paid to clear things up about the rejuvenator mechanism of action. Frequently, the terms rejuvenator and flux oil, or oil (i.e., softening agent) are used as if they were synonymous. According to our knowledge, these two terms refer to substances producing different modifications to the aged bitumen: they can decrease the viscosity (softening agents), or, in addition to this, restore the original microstructure (real rejuvenators). In order to deal with the argument in its entirety, the bitumen is investigated in terms of chemical structure and microstructural features. Proper investigating tools are, therefore, needed to distinguish the different mechanisms of action of the various types of bitumen, so attention is focused on recent research and the use of different investigation techniques to distinguish between various additives. Methods based on organic synthesis can also be used to prepare ad-hoc rejuvenating molecules with higher performances. The interplay of chemical interaction, structural changes and overall effect of the additive is then presented in terms of the modern concepts of complex systems, which furnishes valid arguments to suggest X-ray scattering and Nuclear Magnetic Resonance relaxometry experiments as vanguard and forefront tools to study bitumen. Far from being a standard review, this work represents a critical analysis of the state-of-the-art taking into account for the molecular basis at the origin of the observed behavior. Furnishing a novel viewpoint for the study of bitumen based on the concepts of the complex systems in physics, it constitutes a novel approach for the study of these systems.