This study presents a method for the fabrication of solvent-resistant poly(dimethylsiloxane). (PDMC) microfluidic devices by coating the microfluidic channel with on hybrid inorganic/organic polymer (HR4). This modification. dramatically increases the resistance of PDMS microfluidic channels to various solvents, because it leads to a significant reduction in the rate of solvent absorption and consequent swelling. The compatibility of modified PDMS with a wide range of solvents is investigated by evaluating the swelling radio measured through eight changes in a standard block. The HR4-modified PDMS microfluidic device can be applied to the formation of water-in-oil (W/O) and oil-in-water (O/W) emulsions.. The generation of organic solvent droplets with high monodispersity in the microfluidic device without swelling problems is demonstrated. The advantage of this proposed method is that it can be used to rapidly fabricate microfluidic devices using the bulk properties of PDMS, while also increasing their resistance to various organic solvents. This high compatibility with a variety of solvents of HR4-modified PDMS can expand the application of microfluidic systems to many research fields.