Hydrogenation catalysis is dominated by transition metals, but interest in alternative catalysts has been growing over recent years. Herein, a transition-metal-free catalyst is discussed consisting of carbon supported NaAlH4 as a selective catalyst for hydrogenation. This is illustrated using a range of substrates, and in more detail for the case of diphenylacetylene. Catalytic activity depends on the solvent utilized; in cyclohexane the activity is 2.3 mol (DPA) mol(-1) (NaAlH4) h(-1) at 100 bar H-2, 150 degrees C with a slight preference for the formation of trans-stilbene. The catalyst selectivity is influenced by the loading, yielding a high selectivity toward the thermodynamically less stable cis-stilbene at low catalyst loadings. This proof of principle shows promise for using metal hydrides based on earth-abundant elements as effective hydrogenation catalysts. (C) 2016 Elsevier Inc. All rights reserved.