Electrocatalytic energy conversion between electricity and chemical bonding energy is realized through redox reactions with multiple charge transfer steps at the electrode-electrolyte interface. The surface atomic structure of the electrode materials, if appropriately designed, will provide an energetically affordable pathway with individual reaction intermediates that not only reduce the thermodynamic energy barrier but also allow an acceptably fast kinetic rate of the overall redox reaction. As one of the most abundant and stable forms, oxides of transitional metals demonstrated promising electrocatalytic activities towards multiple important chemical reactions. In this topical review, we attempt to discuss the possible avenues to construct the electrocatalytic active surface for this important class of materials for two essential chemical reactions for water splitting. A general introduction of the electrochemical water splitting process on the electrocatalyst surface with applied potential will be provided, followed by a discussion on the fundamental charge transfers and the mechanism. As the generally perceived active sites are chemical reaction dependent, we offer a general overview of the possible approaches to construct or create electrocatalytically active sites in the context of surface atomic structure engineering. The review concludes with perspectives that summarize challenges and opportunities in electrocatalysis and how these can be addressed to unlock the electrocatalytic potentials of the metal oxide materials.