Despite innovations in the synthesis protocol of nanoparticles (NPs), the size distribution and uniformity of particles still remain as crucial attributes. Homogeneous and rapid nucleation is a critical phenomenon to obtain monodisperse nanoparticles. Herein, we have carried out the synthesis of metal nanoparticles in a customized microfluidic (MF) chip, with 18 omega-shaped micromixers, by using glycerol as a promising green solvent and reducing agent at various concentrations (10-80%), and simultaneous comparison of the results from batch synthesis. Initially, mixing characterization for 10-80% glycerol was obtained by adjusting the Peclet (Pe) number. Further, the effect of the Pe number, time, and concentrations of polyvinylpyrrolidone, metal source, and glycerol on the NP size was investigated. Interestingly, the experimental findings depicted that by varying different parameters, the spherical nanoparticles with an average ultrasmall particle diameter of <2 nm were obtained at all glycerol concentrations (10-80%), as compared to batch synthesis (giving a yield of ∼10-fold larger particles). The mixing efficiency in this MF chip design was analyzed by using a fluorescent dye in glycerol, while the particle morphology and size were characterized by using dynamic light scattering, transmission electron microscopy, and ultraviolet-visible spectroscopy. Hence, compared to the conventional benchtop-assisted NP synthesis, this study unveils the significant effect of the microfluidic technique on the synthesis of ultrasmall and homogeneous nanoparticles in a single step, using an environmentally friendly solvent.