Vapour-driven solutal Marangoni effects have been studied extensively due to their potential applications, including mixing, coating, and droplet transport. Recently, the absorption of highly volatile organic liquid molecules into water droplets, which drives Marangoni effects, has gained significant attention due to its intricate and dynamic physical behaviours. To date, steady-state scenarios have been considered mainly by assuming the rapid establishment of vapour–liquid equilibrium. However, recent studies show that the Marangoni flow arises even under uniform vapour concentration, and requires a considerable time to develop fully. It indicates that the vapour–liquid equilibrium takes longer to establish than was previously assumed, despite earlier studies reporting that vapour molecules instantly adsorb on the interface, highlighting the importance of observing transient flow patterns. Here, we experimentally and numerically investigate time-dependent flow structures throughout the entire lifetime of a droplet in ethanol vapour environments. Under two distinct vapour boundary conditions of uniform and localised vapour distributions, a significant flow structure change consistently occurs within the droplet. The time-varying ethanol vapour mass flux from numerical simulation reveals that the flow transition is caused by the high vapour absorption flux at the droplet contact line, due to the geometric singularity there. Based on the detailed analysis of the surface tension gradient along the droplet interface, we identify that the flow transition occurs before and after the vapour–liquid equilibrium is achieved at the droplet contact line, which induces the flow direction change near the contact line.