Nitroarenes are stable, low‐cost, and readily available starting materials. The directly utilize nitroarenes in synthetically valuable C−N bond formation is of great significance, because the pre‐reduction step to corresponding amines can be avoided. Previously, phosphines and carbon monoxide (CO) are the most widely used reductants in the reductive cyclization or/and carbonylation of nitroarenes. Currently, much attention has been attracted to organosilanes as new potential reducing agents, not only because they are inexpensive, easy‐to‐handle, and mild reagents, but also various novel reaction models of nitroarenes have been explored. In this review, we mainly summarize the recent progress on the reductive coupling of nitroarenes by using organosilanes as the end reductants. We hope that a deep understanding of the reaction model and underlying working mechanism can provide a timely guideline for researchers who are interested in this fantastic area, leading to further exploration of practical and efficient reductive coupling of nitroarenes for C−N bond formation and N‐heterocycle synthesis.