Rhodium(III) azide half‐sandwich complexes of general formula [Rh(Cp*)(N3)(bpyR,R)]CF3SO3 with R = H, OCH3 were prepared in three steps in an overall yield of 55–65 %. Their stability strongly depends on the 4,4′‐substituent on the 2,2′‐bipyridine (bpy) ligand and increases in the order COOCH3 < H < OCH3. Consequently, no stable product could be isolated for the complex with the methyl ester substituent. The title compounds easily underwent cycloaddition reactions with ethyl 4,4,4‐trifluoro‐2‐butynoate in acetonitrile at room temperature in the absence of catalyst. The resulting triazolate products were simply isolated by precipitation in 65–75 % yield. The trifluoromethyl group enabled facile monitoring of the reaction by 19F NMR spectroscopy. Kinetic studies with solution IR spectroscopy revealed pseudo‐first‐order rate constants of 2.4 to 3.8 × 10–3 s–1, and the reactions were accelerated by the presence of electron‐donating groups at the 4,4′‐position of the bpy coligand. These values are of a similar magnitude as those for the Staudinger ligation utilized for bio(macro)molecule functionalization.