Luminescent coordination polymers can be potential chemosensors and extensive efforts are being devoted to improve their selectivity and sensitivity. In this work, we report a new kind of fluorene‐based Tb‐CP, Tb4L6·7DMF·5H2O (Tb4L6, H2L = 4,4′‐(9,9‐dimethyl‐9H‐fluorene‐2,7‐diyl)dibenzoic acid), showing 2D network and strong blue emission. Meanwhile, Tb4L6 exhibits excellent selectivity and sensitivity for picric acid (PA). The quenching constant (Ksv) of Tb4L6 is equal to 4.5 × 104 L/mol during the concentration range of 0–30 μmol/L, which approaches the best reported CPs‐based on PA sensor up to now. Moreover, we went into depth on the possible mechanisms of luminescence quenching.