Porous sol-gel silica monoliths are prepared using PMMA nanoparticles, 60 nm in diameter, as sacrificial templates. The pore-structure of the calcined pellets is investigated through nitrogen adsorption to assess the evolution of the porosity when varying the amount of porogen. The latex templated monoliths present a well defined spherical extrinsic porosity and an intrinsic microporosity due to preparation process. As a result of a careful analysis of the adsorption hysteresis, we identify a percolation threshold of the spherical porosity around 30% volume fraction. This phenomenon, similar to the percolation previously observed in latex-templated silica films, opens the way to the use of latex-templated porous silica monoliths with a tailorable and reliable pore structure.