The conversion of biomass compounds into fuels and chemicals is an important step towards a more sustainable future. This work combines results from model surfaces and powder catalysts to demonstrate Cu-modified molybdenum nitride (Cu/Mo2N) as a selective catalyst for dehydrogenation of the biomass model compounds, ethanol and isopropanol. Results from model surfaces showed that while Mo2N led to unselective decomposition via both dehydrogenation and dehydration, the addition of Cu increased the dehydrogenation activity and selectivity. DFT calculations showed how Cu influenced the structures of active sites, adsorbate interactions, and thus the product selectivity. Batch reactor studies on corresponding powder catalysts confirmed the trend that Cu modification increased dehydrogenation activity, and in situ X-ray absorption spectroscopy elucidated the Cu oxidation state under reaction conditions. This work demonstrates a strategy for promoting dehydrogenation over Mo2N-based catalysts, as well as the feasibility of using model surfaces to guide the design of industrially relevant catalysts.