The production of hydrogen peroxide H2O2, as an important commodity chemical, attires the attention towards greener processes such as the direct synthesis from hydrogen H-2 and oxygen O-2, the selectivity being the biggest challenge. Since this reaction is structure-sensitive, the design of appropriate catalystsis required. We propose a novel method to prepare hierarchically porous Pd/SiO2 catalyst by combination of miniemulsion polymerisation to prepare a Pd-containing latex template and sol-gel synthesis in controlled conditions to tailor the silica porosity. The final material displayed a surface area of 711 m(2)g(-1) and a total pore volume of 0.93 cm(3)g(-1). The catalyst was evaluated with different pre-treatments in the direct synthesis of H2O2, where it exhibited structural resistance at the reaction conditions and a stable selectivity of 46 +/- 1% towards H2O2. (C) 2016 Elsevier B.V. All rights reserved.