This paper reports on a novel microfluidic technique for the fabrication of microspheres of synthetic polymers including poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(lactic acid) (PLA), and polystyrene (PS). The polymers are dissolved in tetrahydrofuran (THF) and the method is based on the diminished solubility of THF in a 20% (w/v) NaCl solution which allows the formation of droplets of the polymer solution. These polymer solution droplets are generated in a microfluidic system and their desolvation is accomplished within seconds by allowing the droplets to rise by buoyancy through a NaCl solution with a concentration lower than 15%. The size and morphology of the resultant polymer microspheres have been investigated by optical and scanning electron microscopy. Apart from the elimination of the use of highly toxic solvents as in conventional methods for manufacturing of polymer microspheres, the newly developed technique has the advantages of providing faster desolvation of the polymer solution droplets and a higher yield of microspheres compared to emulsification-based techniques.