Following the intention to correlate electrocatalytic and electronic behaviour of metallic surfaces, the electronic behaviour of PtxMe1-x (Me = Pd, Cu, Au, In, Sri, Pb, Bi) monolayers over Pt(111) surface were examined in dependence of mole fraction of platinum. Calculation technique based on density functional theory was used. The results of two different calculation methods used to estimate work function agree very well mutually and with the experimentally obtained data, when available. In addition, the populations of valence orbitals as well as the energies of cl-band centres of surface Pt atoms were calculated, and compared with existing literature data. It was shown that one can tune surface electronic, and substantially, chemical properties by controlling the amount of solute elements in surface layer. Obtained results, in combination with previously established models, could be used as a starting point in a search for new catalysts and electrocatalysts. (C) 2009 Elsevier B.V. All rights reserved.