A novel monoanionic tetradentate N4 ligand (F5DPPy) based on a dipyrromethene skeleton as a molecular platform and decorated with pyridine rings at the 1‐ and 9‐positions of the dipyrrin motif has been prepared and characterized. Interestingly, although this ligand is weakly fluorescent, it presents a chelation‐enhanced fluorescence effect of around 150 times upon coordination to ZnII. Time‐dependent (TD) DFT calculations reproduce nicely the spectroscopic features of both the ligand and the complex, and analysis of the electron density redistribution in the excited state suggests that a better orbital overlap of the HOMO and LUMO in F5DPPyZnCl compared with F5DPPy is responsible for the more intense transitions observed with the former system. As such, this ligand opens interesting perspectives in the design of ratiometric sensors. A new N4 ligand featuring a dipyrrin skeleton decorated with 2‐pyridyl groups was synthesized and characterized. Upon zinc complexation, a 150‐fold chelation‐enhanced fluorescence was observed, which was rationalized by DFT calculations. This result opens interesting perspectives toward the use of this type of ligands as ratiometric sensors, following the example of their famous BODIPY analogues.