N-2-aryl-1,2,3-triazole derivatives were synthesized as new ligand systems for the construction of photoluminescent active metal–organic frameworks (MOFs). Crystal structures revealed that the five-membered triazoles show an unsymmetrical conformation with the two C4,C5-substituted benzenes adopting a “twisted-planar” geometry. As a result, a MOF constructed from this ligand exhibited cross-layer interactions with improved water stability (at 100 °C for 24 hours). Furthermore, enhanced photoluminescence emissions were observed upon the formation of MOF structures (Φ up to 30%), suggesting the potential applications of these photoactive porous materials through this new ligand design.