Discussed are the recent experimental and theoretical results on palladium-based catalysts for selective hydrogenation of alkynes obtained by a number of collaborating groups in a joint multi-method and multi-material approach. The critical modification of catalytically active Pd surfaces by incorporation of foreign species X into the sub-surface of Pd metal was observed by in situ spectroscopy for X=H, C under hydrogenation conditions. Under certain conditions (low H2 partial pressure) alkyne fragmentation leads to formation of a PdC surface phase in the reactant gas feed. The insertion of C as a modifier species in the sub-surface increases considerably the selectivity of alkyne semi-hydrogenation over Pd-based catalysts through the decoupling of bulk hydrogen from the outmost active surface layer. DFT calculations confirm that PdC hinders the diffusion of hydridic hydrogen. Its formation is dependent on the chemical potential of carbon (reactant partial pressure) and is suppressed when the hydrogen/alkyne pressure ratio is high, which leads to rather unselective hydrogenation over in situ formed bulk PdH. The beneficial effect of the modifier species X on the selectivity, however, is also present in intermetallic compounds with X=Ga. As a great advantage, such PdxGay catalysts show extended stability under in situ conditions. Metallurgical, clean samples were used to determine the intrinsic catalytic properties of PdGa and Pd3Ga7. For high performance catalysts, supported nanostructured intermetallic compounds are more preferable and partial reduction of Ga2O3, upon heating of Pd/Ga2O3 in hydrogen, was shown to lead to formation of PdGa intermetallic compounds at moderate temperatures. In this way, Pd5Ga2 and Pd2Ga are accessible in the form of supported nanoparticles, in thin film models, and realistic powder samples, respectively.