A matter of catalyst: Azole compounds can be directly alkylated with N‐tosylhydrazones that bear unactivatedalkylgroups (see scheme; phen=1,10‐phenanthroline, Ts=p‐toluenesulfonyl). Nickel catalysis enables the introduction of simple secondary alkyl chains into benzoxazole compounds, whereas the alkylation of 5‐aryloxazoles and benzothiazole is possible by using a cobalt catalyst.