© 2018 The Author(s) Pd nanoparticles supported on SiO 2 , Si 3 N 4 and Al 2 O 3 were studied to examine the effect of particle size and support type on the hydrogenation of 1,3-butadiene. Pd nanoparticles were produced using a reverse micelle method resulting in particles with a remarkably small particle size distribution (σ < < 1 nm). The support type and particle size were observed to affect both catalytic activity and product selectivity. All catalysts showed a decrease of their activity with time on stream, paired with an increase in selectivity to butenes (1-butene and cis/trans-2-butene) from a product stream initially dominated by n-butane. In situ XAFS demonstrated a correlation between the formation of palladium hydride and n-butane production in the early stages (~ 1 h) of reaction. The extent of palladium hydride formation, as well as its depletion with time on stream, was dependent on both particle size and support type. Metallic Pd was identified as the species selective towards the production of butenes.