Homogeneous catalysts are highly active and selective compared to heterogeneous catalysts due to their solubility in reaction media, following molecular mechanisms. However, heterogeneous catalysts are thermally stable and, in many cases, economically viable but less active and selective due to surface reactions with less abundant active sites. There are various attempts to make heterogeneous catalysts as active and selective as homogeneous by incorporating sufficient electrophilicity. This chapter discusses a conceptual journey of the development of electrophilic catalysts which includes stabilization of metal NPs, dendrimer approach, monodisperse metal NPs, and the introduction of electrophilicity by treatment with oxidants. In certain cases, heterogeneous catalysts showed better activities compared to homogeneous protocols. This chapter is dedicated to the memory of Professor Gábor A. Somorjai (1935–2025), for his contribution to modern surface science and catalysis.