Inverted catalytic systems, in which metal oxide films are deposited on top of metallic substrates, present significant potential for catalysis, because of the ability to enhance the metal/metal oxide interface. Most of the reported methods for synthesizing these structures involve thermal treatment of the oxide film, which presents a significant challenge for reducible metal oxides, because of strong metal-oxide interactions, often leading to blocking of metal active sites. Herein, a solution-phase method is developed to synthesize Pd@TiO2 inverted catalytic structures where encapsulation is conducted at room temperature using a sol–gel reaction of Ti alkoxide precursors to circumvent thermal treatment. We show that key synthesis parameters can be used to control the desired physical properties of the inorganic encapsulating film to achieve enhanced catalytic performance. Significant effects on catalytic performance toward a probe reaction, hydroisomerization of 1-hexene, are reported as a function of th...