In this study, we present simple microfluidic approach for the synthesis of monodisperse microcapsules by using droplet-based system. We generate double emulsion through single step in the microfluidic device having single junction while conventional approaches are limited in surface treatment for the generation of double emulsion. First, we have injected disperse fluid containing FC-77 oil and photocurable ethoxylated trimethylolpropane triacrylate (ETPTA) and water containing 3 wt% poly(vinyl alcohol) (PVA) as continuous phase into microfluidic device. Under the condition, we easily generate double emulsion with high monodispersity by using flow focusing. The double emulsion droplets are transformed into microcapsules under the UV irradiation via photopolymerization. In addition, we control thickness of double emulsion’s shell by controlling flow rate of ETPTA. We also show that the size of double emulsions can be controlled by manipulation of flow rate of continuous phase. Furthermore, we synthesize microcapsules encapsulating various materials for the application of drug delivery systems.