In this work, we present a general sol-gel protocol for the synthesis of highly porous monolithic transition metal borides via carbothermal conversion of the organic/inorganic interpenetrating networks (IPNs). The formation of organic/inorganic IPNs is clearly demonstrated by simple oxidation and boiling water treatment. A series of transition metal boride porous monoliths, including CrB2, ZrB2, TiB2, Cr3C2/CrB, and ZrB2/ZrC with porosities ranging from 70% to 85% and pore sizes ranging from 0.5 to 35 mu m, have been prepared. In each case, a porous hybrid monolith is obtained by drying the wet gel under ambient pressure. It is believed that the formation of organic/inorganic IPNs strengthens the gel network, so that it can withstand the severe changes during desiccation to give out a monolithic xerogel. Samples are characterized by TG-DSC, XRD, SEM, EDS, TEM, BET, and MIP, and the ceramic monoliths are shown to be well defined and rather homogeneous.