The introduction of aggregation-induced emission (AIE) moieties into polymers results in smart materials with AIE characteristics, expanding their scope of applications. Herein, well-defined polymers with controlled molecular weight, low dispersity, and high end-group fidelity are produced via copper(0)-mediated reversible-deactivation radical polymerizations (Cu(0)-RDRPs). An AIE-containing initiator tetraphenylethene bromoisobutyrate (TPEBIB) has been synthesized, fully characterized, and utilized for the construction of different polyacrylate homopolymers and block copolymers bearing the TPE group with a range of molecular weights and architectures. All of the polymers exhibited AIE behavior. Notably, the hydrophobic TPE-poly(tert-butyl acrylate) (TPE-PtBA)-containing block copolymers are transformed to TPE-poly(acrylic acid) (TPE-PAA)-based amphiphilic copolymers by facile deprotection, enabling pH-tunable self-assembly in aqueous media to give fluorescent nanoparticles with various sizes. The low cytotoxicity, high specificity, and excellent photostability render them promising candidates as lysosome-specific probes in biological imaging applications.