Since the seminal discovery of phenyl azide by Grieß in 1864, a variety of organic azides (R-N3) have been developed and extensively studied. The amenability of azides to a number of reactions has expanded their utility as building blocks not only in organic synthesis but also in bioorthogonal chemistry and materials science. Over the decades, it has been demonstrated that the reactions of main group compounds with azides lead to diverse N-containing main group molecules. In view of the pronounced progress in this area, this review summarizes the reactions of main group compounds with azides, emphatically introducing their reaction patterns and mechanisms. The reactions of forming inorganic nitrogen species are not included in this review.