© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chemical transformation of 9-azidophenanthrene on the Ag(111) surface was studied by nc-AFM in UHV. High-resolution imaging supported by first-principle calculations revealed the structure of the final products that originated from a common and elusive 9-phenanthryl nitrenoid intermediate chemisorbed on the Ag(111) surface. A formal nitrene insertion into the C−H bond along with its dimerisation and hydrogenation were identified as main reaction channels. Thus, the ability of aryl azides to form covalent σ- and π-bonds between their transformation products on a solid surface was demonstrated at a single-molecule level.