Ordered mesoporous metal oxides were prepared from a silica hard template. Two stabilization approaches for preparing high temperature ordered mesoporous structures were presented and their functionality as electrodes for intermediate temperature solid oxide fuel cells (IT-SOFCs) was proven. Firstly, nickel based mesoporous cermets were synthesized and characterized by using a scaffolding approach. A compact unit is synthesized by a multi-impregnation step. The nano-structure is kept stable up to 1200 °C (electrode-electrolyte attachment temperature) due to the intimate connection between the ceramic and the metal networks. Moreover, virtually no degradation of the microstructure and the electrochemical performance was demonstrated for the cermet after 200 h of test at 800 °C in a humidified Ar-5 % H2 atmosphere. A second thermal stabilization approach was performed for open 3D mesoporous structures, by the partial crystallization of the mesoporous oxide inside the template, reaching the so-called self-limited grain growth regime. The self-supported replicas maintain the periodic mesoporous structure and a high surface area up to 1000 °C. SDC scaffolds for symmetrical cells were fabricated. Long-term impedance measurements performed with SSC-infiltrated on the SDC scaffolds as symmetrical cells revealed an area specific resistance (ASR) improvement by ~ 45 %, up to an ASR value of 0.07 Ω cm2 during the first 200 hours. The proposed methodologies represent a step forward towards the implementation of mesostructures in applications where high thermal stability is required such as solid oxide fuel/electrolysis cells, gas separation membranes or high temperature catalysis.