The kinetics of higher alcohol synthesis was investigated using a hydrotalcite-derived Co-Cu-based catalyst aiming at a deeper understanding of the complex reaction network. At steady state similar chain growth probabilities of about 0.4 according to the Anderson-Schulz-Flory distribution were observed for alcohols, hydrocarbons and olefins indicating common intermediates. Alkanes were found to be formed consecutively from primarily formed olefins. The observed decrease of the selectivities to alcohols with increasing CO conversion at higher temperatures and higher residence times is ascribed to an increased availability of adsorbed atomic hydrogen, which decreases the saturated coverage of CO-derived CxHyOz species favoring hydrocarbon formation. Correspondingly, reaction orders of 0 and 0.8 for CO and H-2, respectively, were derived based on a power-law approach including an apparent activation energy of 140 kJ mol(-1). A reaction network based on the CO insertion factor was established, in which the competing reactions beta-hydrogen elimination, chain growth and CO insertion proceed from common adsorbed CxHy intermediates. Selective higher alcohol formation was favored at low temperatures and short residence times, high pressures and a moderate H-2:CO ratio of 1 requiring a compromise between conversion and selectivity. (C) 2020 Elsevier Inc. All rights reserved.