Sensitisation of Ln 3+ PL in 3-LnLnʹ was studied, where excitation of ancillary ligands could be used to selectively induce emission from one or both Ln 3+ ions via complex and directional ET pathways which are of interest for optical and sensing purposes. Variations in the Stark sublevel splitting of Yb 3+ PL emission caused by the different coordination environments of Yb 3+ in 3-YbEu and 3-DyYb further support the binding site selectivity. Unusually, not only is emission observed in 1-Ln and 3-LnLnʹ from lanthanides which are directly coordinated by a radical ligand, but the radical ligand in both 1-Ln and 3-LnLnʹ coordinates via its open-shell semiquinone O,Oʹ site, and that emission results after direct excitation of the radical ligand. Here, pd •-is shown to sensitise PL from both Eu 3+ and Yb 3+ , providing an unusual example of participation of a doublet state in sensitisation of lanthanide PL.