Fluorescent drug delivery systems have received increasing attention in cancer therapy because they combine drug delivery and bioimaging into a single platform. For example, polymers with aggregation-induced emission (AIE) fluorophores, such as tetraphenylethylene (TPE), have emerged as an elegant choice for drug delivery/bioimaging applications. In this work, we report one-pot sequential organocatalytic ring-opening polymerization of ε-caprolactone (CL) and ethylene oxide (EO) using TPE-(OH)₂ as a difunctional initiator, in the presence of a t-BuP₂/TEB Lewis pair (catalyst), in THF at room temperature. Two well-defined triblock copolymers with inverse block sequences, TPE-(PCL-b-PEO)₂ and TPE-(PEO-b-PCL)₂, were synthesized by altering the sequential addition of CL and EO. The physicochemical properties, including hydrodynamic diameter, morphology, and AIE properties of the synthesized amphiphilic triblock copolymers were investigated in aqueous media. The block copolymer micelles were loaded with anticancer drugs doxorubicin and curcumin to serve as drug delivery vehicles. In vitro studies revealed the accelerated drug release at lower pH (5.5), which mimics the tumor microenvironment, different from the physiological pH (7.4). In vitro cytotoxicity studies demonstrated that the neat block copolymer micelles are biocompatible, while drug-loaded micelles exhibited a significant cytotoxic effect in cancer cells. Cellular uptake, examined by confocal laser scanning microscopy, showed that the block copolymer micelles were rapidly internalized by the cells with simultaneous emission of TPE fluorophore. These results suggest that these triblock copolymers can be utilized for intracellular bioimaging.