The ability to create aqueous suspended stable nanoparticles of the hydrophobic homopolymer poly(ϵ-caprolactone) end-functionalized with coumarin moieties (CPCL) is demonstrated. Nanoparticles of CPCL are prepared in a continuous manner using nanoprecipitation. The resulting nanoparticles are spherical in morphology, about 40 nm in diameter, and possess a narrow size distribution and excellent stability over 4 months by repulsive surface charge. Nanoparticle size can be easily controlled by manipulating the concentration of CPCL in the solution. The interparticle assembly between the nanoparticles can be reversibly adjusted with photoirradiation due to photoinduced [2 + 2] cyclodimerization and cleavage between the coumarin molecules. In addition, the CPCL nanoparticles show significant cellular uptake without cytotoxicity, and the intrinsic fluorescence of the coumarin functional group permits the direct detection of cellular internalization.