This paper reports a novel combination of hydrophilic/hydrophobic materials for the evolution of liquid manipulation. Droplet generation based on a hydrophilic/hydrophobic mechanism is a promising method for highly accurate liquid manipulations. Although several droplet manipulation devices utilizing hydrophilic/hydrophobic patterns have been reported, it has been difficult to split fluid into droplets solely through hydrophilic/hydrophobic patterns in a microchannel. In this study, a material combination for fabricating hydrophilic/hydrophobic patterns was investigated and their wettability difference was enhanced for droplet generation. To improve hydrophilicity, we attempted to increase the surface area of silicon oxide through pulsed plasma chemical vapor deposition (PPCVD). To improve hydrophobicity, the damage to the hydrophobic patterns in the fabrication process was reduced. We successfully enhanced the difference in contact angles from 54.3° to 86.6° by combining the developed hydrophilic material and hydrophobic material. The developed material combination could successfully split fluid into a quantitative droplet of 14.1 nL in a microfluidic chip. Because the developed hydrophilic/hydrophobic combination enables the formation of a droplet with desirable shape in microchannels, the developed hydrophilic/hydrophobic combination is a promising component for lab-on-a-chip applications.