Kinetic analysis for the acid-catalyzed dimerization of C-4 olefins was performed in a batch reactor, and a suitable rate model was developed. It was further used in the rate-based simulation model of a continuous reactive distillation (RD) column. The results obtained were compared with the experimental observations made on a pilot-scale high-pressure RD column. An important outcome of the present work is that RD can be used efficiently to enhance the selectivity of C-8 dimers, thereby avoiding the formation of trimers and tetramers. The use of polar components (such as water or alcohols), as selectivity enhancers, is not necessary.