Reactive dividing wall columns (RDWC) are a special type of distillation column that allow for the targeted realization of chemical reactions and the separation into multiple product fractions in one shell. However, despite their huge economical and ecological potentials for certain fields of application, this innovative technology has not found its way into industrial production processes yet. The very limited availability of experimental research studies verifying the prediction capabilities of respective modeling concepts for this type of distillation column might be one decisive reason for that. Therefore, the present study puts its focus on the detailed comparison between experimental operation of RDWC and the corresponding simulation results for steady-state. For the first time, the mentioned comparison is carried out for a chemical system with non-negligible side reactions. It is shown that even for this highly complex system, the mathematical model is capable of predicting the column operation. (c) 2016 American Institute of Chemical Engineers AIChE J, 63: 1036-1050, 2017