Higher alcohol synthesis from syngas is studied over K/MoS2 domains supported on mesoporous carbon (C), mixed MgAl oxide (MMO), or mixtures thereof. While the carbon support offers high ethanol productivity, the MMO support yields enhanced C3+OH selectivity. MoKMMO-C, whereby Mo is initially contained on MMO then ground with carbon, behaves similar to the parent MoKMMO catalyst, as Mo on MMO has limited mobility during reaction. In contrast, on MoKC-MMO, significant Mo migrates from C to MMO during reaction, giving reactivity associated with Mo species on both supports (high C3+OH selectivity and productivity). MoS2 domain structures are correlated with the selectivity of the catalysts (C3+OH selectivity double MoS2 layers, total hydrocarbon selectivity single MoS2 layers). This study advances the understanding of the support's effect on structure reactivity relationships for this family of catalysts and introduces a new catalyst composition with desirable reactivity. (C) 2015 Elsevier Inc. All rights reserved.