We review recent work from our laboratory on a materials-by-design approach to the development of new electrocatalysts. Model systems like the Pt(lll) single crystal electrode and well-characterized Pt alloys are studied to create a link between the microscopic level of understanding the bonding and reactivity of adsorbates and the macroscopic measurements of kinetic rate and thermodynamic properties of the reacting system. The knowledge is then used to create tailor-made surfaces, usually using UHV surface processing techniques, having the required microscopic structure to produce the desired catalytic properties. Finally, after optimizing the tailor-made surface, the real-life catalyst is synthesized using chemistry that recreates, to the greatest extend possible, the tailor-made surface. We have demonstrated the successful development of a new GO-tolerant catalyst using this strategy.