We report a novel approach for the on-line characterization of nucleation and growth kinetics of lead sulfide (PbS) quantum dots using droplet-based microfluidics. Monodisperse NIR-emitting PbS with optical bandgap between 680 to 1200 nm can be formed rapidly using two reaction schemes at different operating temperatures between 70 and 130°C and the temporal evolution of the absorption and fluorescence spectra are monitored in real-time using a microfluidic platform with an on-line absorption and fluorescence optical system. Therefore, this microfluidic platform is able to provide quantitative information on a millisecond (ms) time frame regarding the size, size distribution, concentration and emission characteristics of the generated nuclei and particles. To our knowledge, this represents the first microfluidic approach for the study of the nucleation and growth in high-temperature colloidal crystallization using in-situ absorption and photoluminescence spectroscopy.