α‐Ferrocenylalkylation of azoles or S‐nucleophiles with FcCH(R)OH (Fc = ferrocenyl) can be accomplished under acid‐free conditions as one‐pot process via an intermediate formation of the α‐ferrocenylalkyl carbonates FcCH(R)OC(O)OEt. The reaction allows the alkylation of acid sensitive substrates like imidazole derivatives or sodium N,N‐diethyldithiocarbamate. The reaction with ambident azoles proceeds as the N‐alkylation. Some α‐ferrocenylalkyl azoles were found to exhibit plant growth stimulating or herbicidal effects on corn seeds or act as the herbicide safeners against sulfonylurea herbicides.