Phase segregation triggered by selective evaporation can emerge in multicomponent systems, leading to complex physicochemical hydrodynamics. Recently, Li et al. (Phys. Rev. Lett., vol. 120, 2018, 224501) and Kim & Stone (J. Fluid Mech., vol. 850, 2018, pp. 769–783) reported a segregative behaviour (i.e. demixing) in an evaporating binary droplet. In this work, by means of experiments and theoretical analysis, we investigate the flow dynamics after the occurrence of the phase segregation. As example, we take the 1,2-hexanediol–water binary droplet system. First, we reveal experimentally the overall physicochemical hydrodynamics of the evaporation process, including the segregative behaviour and the resulting flow structure close to the substrate. By quantifying the evolution of the radial flow, we identify three successive life stages of the evaporation process. At Stage I, a radially outward flow is observed, driven by the Marangoni effect. At the transition to Stage II, the radial flow reverses partially, starting from the contact line. This flow breaks the axial symmetry and remarkably is driven by the segregation itself. Finally at Stage III, the flow decays as the evaporation ceases gradually. At this stage, the segregation has grown to the entire droplet, and the flow is again controlled by the Marangoni effect. The resulting Marangoni flow homogenizes the distribution of the entrapped volatile water over the whole droplet.