This work reports on the preparation and optical characterization of two metal-organic frameworks (MOFs) based on strontium ions and 2-amino-1,4-benzenedicarboxylate (NH2-bdc) ligand: i.e., [Sr(NH2-bdc)(DMF)]n (1) and {[Sr(NH2-bdc)(Form)]·H2O}n (2) (where DMF = dimethylformamide and Form = formamide). Compound 1 has a 3D architecture built up from the linkage established by NH2-bdc among metal-carboxylate rods, leaving significant microchannels that are largely occupied by DMF molecules coordinated to strontium centers. The solvent molecules play a crucial role in the photoluminescence (PL) properties, which has been deeply characterized by diffuse reflectance and variable-temperature emission. Interestingly, both materials present intriguing photoluminescence (PL) properties involving intense short-lived and long-lasting phosphorescence (LLP), though the latter is especially remarkable for compound 2 with a lifetime of 815 ms at low temperature. Conversely, the strong PL shown by 1 may be successfully exploited due to both its luminescent thermochromism observed in the RT to 10 K range and its solvent-dependent PL sensing capacity, imbuing this material with potential activity as a PL thermometer as well as a toluene detector in water solutions.