A new ferrocenylnaphthoxazole [(η 5-C 5H 5)Fe{(η 5-C 5H 4)C(O) N(C 10H 6)}] ( 1) was synthesized under mild conditions. Two mercurated derivatives: ortho-mercurated product [HgCl{(η 5-C 5H 5)Fe[(η 5-C 5H 3)C(O) N(C 10H 6)]}] ( 2) and the product mercurated on the unsubstituted Cp ring [HgCl{(η 5-C 5H 4)Fe[(η 5-C 5H 4)C(O) N(C 10H 6)]}] ( 3) were obtained by the reaction of 1 with mercuric acetate. All the new compounds 1, 2 and 3 were characterized by elemental analyses, IR, NMR, MS spectra and X-ray crystal structure analysis. The crystal structure of 1 extended into a 2D supramolecular network through the intermolecular π–π stacking interaction between the Cp ring and naphthoxazole ring. In the crystal of 2, there exist bridged Cl–Hg bonds, CH(Cp) ⋯ Cl and CH⋯ Hg hydrogen bonds, π–π stacking interactions, which facilitate construction of this complex into a 3D supramolecular structure.