The natural porosity of geopolymers and the simplicity of geopolymer synthesis make them a potential candidate for the formation of highly porous ceramics. Here, the synthesis of highly porous (approximate to 70vol% or more) metakaolin geopolymer is demonstrated using a novel emulsion preparation with one-pot curing and hydrophobization of the interior pores with alkylalkoxysilanes. Using mercury intrusion porosimetry, tailoring of the characteristic percolation pore size is demonstrated over a range of approximate to 200nm to 10m. Using powder X-ray diffraction, reactivity was shown to be decreased versus typical geopolymers, but substantial geopolymerization still occurred and the samples formed cohesive monoliths. Optional calcination under inert conditions allowed for formation of a glassy ceramic with a notable SiC phase, as well as further increasing the porosity by removing the hydrophobic pore coatings.