Guerbet coupling chemistry is a route to oligomerize ethanol into C ₄₊ alcohols. Long chain ethers can be obtained through bimolecular dehydration of these alcohols. Ethers generated from the dehydration of C ₆₊ alcohols produce a fuel that satisfies diesel engine requirements, therefore selective production of C ₆₊ alcohols is of particular interest. The desired hexanol is synthesized through ethanol and butanol coupling, accompanied by the formation of undesired products through several reaction pathways. In this work the coupling of ethanol and butanol has been studied over Cu _0.01Mg _2.99AlO _x to produce C ₆₊ alcohols through Guerbet coupling reactions. Two series of catalytic tests were performed at 325 °C and 300 psig by using either pure ethanol feed or a cofeed ethanol-butanol 70-30 mole%. A kinetic model was developed to predict the product distribution over a wide range of contact times. Kinetic parameters were regressed by coding a routine that included a solution of differential mole balances embedded in an optimization problem. The herein developed kinetic model was integrated in a process simulation flowsheet that models the upgrading of ethanol into C ₆₊ oxygenates. The butanol cofeeding strategy in the simulations was approached by recycling the produced butanol into the coupling reactor. The simulation results reveal that cofeeding butanol into the Guerbet reactor enhances initial production rates of C ₆₊ alcohols, at the expense of fostering production of byproducts from butanol self-coupling. A maximum carbon yield of 82.2% for C ₆₊ diesel fuel precursors can be obtained by minimizing the byproduct production after introduction of a hydrogenation reactor.