2,1,3-Benzothiadiazole (BTD)-containing red emitter was chemically conjugated onto amphiphilic poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PEG-b-PCL) copolymers to form two new fluorophore-conjugated block copolymers (P5 and P7). P5 is a cationic amino group-containing polymer, whereas, P7 is a neutral polymer. The polymers formed micelles in aqueous solution with average diameters of 45 nm (P7) and 78 nm (P5), which were characterized using dynamic light scattering (DLS) and atomic force microscopy (AFM). Cell internalization of the micelles using mouse macrophage RAW 264.7 was investigated. The micelles formed from P5 were endocytosed into the cell's cytoplasm through a non-specific endocytosis process, which was affected by temperature and calcium ions. Micelles formed from P7 could not be endocytosed. The dramatic difference of cell uptake between P5 and P7 indicated the cationic amino groups had a strong influence on the cell internalization to enhance the endocytosis pathway. 3-(4,5-Dimethyl thiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) viability assay was used to evaluate the cytotoxicity of the P5 micelle and no significant toxicity was observed. This study is the first report regarding the synthesis of BTD-conjugated block copolymers and the application of the biomacromolecules for bioimaging.