Luminescent metal-organic frameworks (LMOFs), as one branch of MOFs, have attracted considerable attention in recent years due to their good crystallinity, structural diversity, tunable porosity and easily induced fluorescence emission. Importantly, their photoluminescence (PL) properties can be adjusted by altering metal ions or metal clusters and organic ligands in one hybrid system. Among the various sensing applications, using LMOFs as chemical sensors to detect the explosive and environment pollution causing nitroaromatic compounds (NACs) is an important topic. In this account, we describe the recent advancements in the field of NAC detection by LMOFs based on the triphenylamine (TPA) unit as the π-conjugated fluorophore.