The reaction of dirhodium tetrakis(3,4,5-trialkoxy)benzoates Rh2(B3OCn)4 (n = 10, 14 and 18) with three different dinitrogenated axial ligands (Lax), namely tetrazine (tz), phenazine (phz) and 4,4-bipyridine (bpy) gave rise to three homologous series of mesogenic coordination polymers, [Rh2(B3OCn)4]Lax.