The effects of water on steam rectification, i.e., multi-stage saturated steam distillation, were investigated in a packed column. N-octane-p-xylene and 1,3,5-trimethylbenzene-1,2,4-trimethylbenzene were used as test systems. Both binary systems are nearly ideal systems and insoluble in water, thus the effects of water in steam rectification can be clearly and definitely revealed. Such unpolar organic liquid is named as "oil". The water/oil at column top can be separated and refluxed at different ratio. Compared with conventional rectification, there are some peculiar phenomena in steam rectification. Water greatly enhances the flooding vapor velocity of the rectification, in addition, water plays a predominant role in pressure drop of the packed bed near flooding point. It is clear that liquid water in the packed bed can promote mass transfer of steam rectification, especially for materials with higher viscosity. In a word, steam rectification can be operated at low temperature with good mass transfer. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.