The reactive distillation process for the synthesis of ethylene glycol (EG) can produce multiple steady states, reducing column operability, particularly during start-up. Thus, the operability of this reactive distillation column with multiple steady-state output during start-up is analyzed by dynamic simulation. It can be shown that different steady states can be reached by applying different start-up configurations and/or policies. The transient responses of the reactive distillation column yielding different steady states during start-up operation are shown. The aims are to provide an idea about how a start-up policy/configuration can define the steady state to be achieved and to show the relationships among the critical operating variables in this procedure. Also, some considerations about convenient start-up strategies are outlined.