The feasibility and potential of reactive distillation was studied to evaluate the enhancement in trivalerin selectivity in the esterification of valeric acid with glycerol, using n-octane as an entrainer over sulfated iron oxide catalyst. Effect of process parameters such as entrainer loading, reaction temperature, and reaction time was evaluated. Results have indicated that the selectivity toward trivalerin can be enhanced up to 95.07%, in comparison to batch process (74.80%), using the stoichiometric molar ratio, which describes the novelty of this work. Kinetic models such as pseudo-homogeneous, Eley-Rideal, and Langmuir-Hinshelwood model were used to study the kinetics of the reaction. The Eley-Rideal model supported the proposed mechanism with higher reliability and accuracy, resulting in an activation energy of 23.77 kJ/mol, which is plausibly less, compared to the batch process (27.37 kJ/mol).