A tetraphenylethene (TPE) group that exhibits aggregation‐induced emission is incorporated into the ligand of a Eu(III) complex (TPEEu) to sensitize the excited state of Eu(III). In steady‐state measurements, TPEEu exhibits weak luminescence when dissolved in aqueous solutions even at a high concentration level, but emits strong fluorescence of TPE and phosphorescence of Eu(III) upon binding with bovine serum albumin. With a delay time of 0.05 ms and a gate time of 1.0 ms in time‐resolved measurements, only phosphorescent emission of Eu(III) is observed with a high on/off ratio. Moreover, this probe is successfully used in time‐resolved luminescence imaging to eliminate the background signal from biological autofluorescence without a washing process. This work provides a general strategy in designing Ln(III) complexes for detecting a broad range of biological molecules.