Luminescent Os(II) and Ir(III) complexes containing a tripodal-type structure terminalized with three thiol derivatives are described. The tripod is introduced through derivatization, with a rigid spacer, of a phenanthroline ligand coordinated to the metal ion, and the entire structure possesses axial geometry. The geometry of the complexes combined with the three anchoring sites, the thiol groups, allows the complexes to adopt an almost perpendicular arrangement to the surfaces and the formation of a well-packed monolayer on Au substrates. The photophysical and electrochemical behavior of the complexes is studied in solution and on surfaces. Furthermore, a self-assembled monolayer (SAM) of Os(II) complexes on an ultraflat Au surface is used to fabricate a metal–molecule–metal junction with Au and In Ga eutectic as electrodes. The Os(II) SAM in the tunneling junction exhibits rectification behavior which is opposite in direction to that which we have previously shown for Ru(II) SAMs.