Rh(III)-catalyzed intermolecular chelation-assisted insertion of carbenes derived from α-diazocarbonyl compounds into non-acidic primary sp³ C–H bonds, for the first time, is reported under mild reaction conditions, thus affording a good complement to previous metal-carbenoid-induced primary C(sp³)–H insertion reactions. We believe that this method will open up a new avenue for primary sp³ C–H functionalization with α-diazocarbonyl compounds.