We review systematic experimental and theoretical efforts that explored formation, structure and reactivity of PdZn catalysts for methanol steam reforming, a material recently proposed to be superior to the industrially used Cu based catalysts. Experimentally, ordered surface alloys with a Pd : Zn ratio of approximately 1 : 1 were prepared by deposition of thin Zn layers on a Pd(111) surface and characterized by photoelectron spectroscopy and low-energy electron diffraction. The valence band spectrum of the PdZn alloy resembles closely the spectrum of Cu(111), in good agreement with the calculated density of states for a PdZn alloy of 1 : 1 stoichiometry. Among the issues studied with the help of density functional calculations are surface structure and stability of PdZn alloys and effects of Zn segregation in them, and the nature of the most likely water-related surface species present under the conditions of methanol steam reforming. Furthermore, a series of elementary reactions starting with the decomposition of methoxide, CH(3)O, along both C-H and C-O bond scission channels, on various surfaces of the 1 : 1 PdZn alloy [planar (111), (100) and stepped (221)] were quantified in detail thermodynamically and kinetically in comparison with the corresponding reactions on the surfaces Pd(111) and Cu(111). The overall surface reactivity of PdZn alloy was found to be similar to that of metallic Cu. Reactive methanol adsorption was also investigated by in situ X-ray photoelectron spectroscopy for pressures between 3 x 10(-8) and 0.3 mbar.