The 1D confinement of silicon in the form of a nanowire revives its newness with the emergence of new optical and electronic properties. However, the development of a production process for silicon nanowires (SiNWs) having a high quality crystalline core and exhibiting good stability in solution with effective outer-shell defect passivation is still a challenge. In this work, SiNWs are prepared from a silicon wafer using solution processing steps, and importantly outer-shell-defect passivation is achieved by in situ grafting of organic molecules based on thin films. Defect passivation and the high quality of the SiNWs are confirmed with thin films on glass and flexible plastic substrates. A dramatic enhancement in both the fluorescence lifetime and infrared photoluminescence is observed. The in situ organic passivation of SiNWs has potential application in all low-dimensional silicon devices including infrared detectors, solar cells and lithium-ion battery anodes.