This article presents a recognition mechanism for nitro-explosives by the luminescent metal-organic framework 1 (LMOF-1) with the aid of density functional theory (DFT) and time-dependent density functional theory (TDDFT). The behavior of hydrogen bonding between the LMOF-1 and nitro-explosives in the S1 state is closely associated with the fluorescence properties of the LMOF-1. In our research, we calculated the geometric configuration, 1H NMR and IR spectra of the Complex 2 formed by LMOF-1 and nitrobenzene in the S0 and S1 states. The results showed that the hydrogen bond in the S1 state was increased, which was unfavorable for the luminescence of LMOF-1. Furthermore, the fluorescence rate of LMOF-1 decreased after encapsulating nitrobenzene into it. These calculated results collectively suggest that LMOF-1 is a potential fluorescence sensor for the detection of nitro-explosives. This research was aiming to provide a better understanding of the recognition mechanism by LMOFs for nitro-explosives.