In order to prevent the risk of volatile organic solvent over exposure in the atmosphere, a sensitive sensing device is needed for detection in common workplaces. Silicon nanowires carrying the high surface-bulk ratio as a unique characteristic could be used for volatile organic solvent sensing. This study proposed to create the sensing device through spontaneous electrochemical reaction. In terms of advantages that silicon nanowire array on volatile organic solvent sensing, sensing of diethyl ether revealed the optimal outcome. The study also discussed the relation of organic solvents molecular and the electrons distribution on silicon nanowires surface, to further weight the impact of the effect on sensing sensitivity.