The syntheses of ferrocenylbiphenylisocyanide gold(I) thiophenolato complexes are described. The preparative route starts from ferrocenylphenylbromide and proceeds in six steps to yield the desired gold(I) complexes, (thiophenolato)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)isocyanide} (11) and (thiophenolato)gold{(4′-ferrocenyl-3,5-dimethyl[1,1′]biphenyl-4-yl)isocyanide} (12) in good yields. The synthetic pathways were developed as a first step toward realizing the goal of preparing metallomesogens based on ferrocenyl-polyphenylenes coordinated to gold(I) thiophenolates, in which long chain alkoxy groups are substituted para to sulfur on the phenyl ring. The crystal structures of (chloro)gold{(4 ′ -ferrocenyl[1,1′]biphenyl-4-yl)isocyanide} (9) and 12 are reported. Complex 9 crystallizes in the space group P2 1 /c and 12 crystallizes in P2 1 /n. Complexes 9 and 12 show short intermolecular Au–Au contacts of 3.3765(7)Å and 3.3334(3)Å, respectively.