We developed a synthetic route, based on radical polymerization, to a fluorescent monolithic hierarchically porous polymer composed of extended pi-conjugated triphenylene motifs. A hexa-vinyl cross-linker containing the triphenylene core was synthesized and copolymerized with styrene in the presence of a polylactide macrochain transfer agent to produce a cross-linked block copolymer monolith. Polymerization-induced microphase separation occurred during polymerization in situ, resulting in a disordered bicontinuous morphology of polylactide and cross-linked polystyrenic domains at a nanometer scale. Removal of polylactide generated percolating mesopores with controllable pore size and exposed micropores within the polystyrenic network. A strong bluish fluorescence was observed from the resulting porous monolith, originating from the embedded triphenylene. Fluorescence was quenched upon exposure to a solution of nitroaromatic compounds. Much stronger and faster quenching compared to the nonporous analog was attributed to the improvement in access to the triphenylene group via enhanced diffusion of the analyte through the interconnected mesopores.