We have calculated fundamental properties of pure and hydrogen-covered (010), (101), (100) and (001) surfaces of the low temperature monoclinic phase of LaNbO4 (LN). The (010) surface was the most stable one, exhibiting electronic structure and local geometric configurations similar to bulk. As the first stage of proton migration into the electrolyte, the ability of LN surfaces to split H-2 molecules was probed indirectly by calculating the adsorption energy of H atoms on two of the LN surfaces. H adsorption on the (010) surface was found to be strongly endothermic, and thus cannot contribute much in splitting H-2. The adsorption energy on the relatively unstable (101) surface was on the other hand approximately -0.6 eV, in the right range for surface H-2 to be catalyzed beneficially. H adsorption on this surface was induced by surface states in the band gap of the clean surface. Since the unstable (101) surface is not abundant, the rate of dissociative adsorption of H-2 on the LN surface can be anticipated to be very low. Application of the energies to simple adsorption isotherm calculations for typical proton conducting fuel cells (PCFCs) operating temperatures correspondingly showed very low H coverage, and it is not expected that LaNbO4 surfaces can contribute much to the H-2 activation reaction of a PCFC anode. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.