In this work, the synthesis of tert-amyl ethyl ether (TAEE) from isoamylenes and ethanol by catalytic distillation (CD) is experimentally and theoretically investigated. As the isoamylenes feedstock for pilot-scale experiments, an industrial light gasoline fraction from a fluid catalytic cracking unit was used. Consequently, the feed stream to the CD column consisted of almost 100 components and approximately 20 chemical reactions took place in the column. For modelling purposes, six chemical reactions and 18 components were selected to represent the chemical system. Despite the simplifications carried out in the chemical system, a good agreement between experimental data and simulation results using a non-equilibrium stage model was found. The results presented in this paper show the technical feasibility of TAEE production by CD. However, the mole fraction of TAEE in the bottom stream of the column was only 24% due to the presence of heavy inert components in the column feed. The experimental conditions must be carefully selected, because TAEE decomposition and a high by-products formation occurred if high pressures or D/F ratios were used during the column operation. (C) 2012 Elsevier B.V. All rights reserved.