The use of [MIII(ox)3]3− (MIII=Ru, Rh) complexes as building blocks for hybrid molecular materials is highlighted with two different synthetic approaches. The first strategy is the combination of organic donors and [RuIII(ox)3]3− units, resulting in the radical salt of formula TTF3[Ru(ox)3]·0.5EtOH·4H2O (1) which shows coexistence of paramagnetism and semiconducting properties. The second approach is the synthesis of extended 2D bimetallic oxalato-bridged networks of general formula [FeCp2*][MIIRh(ox)3] in which paramagnetic layers of decamethylferricinium cations are alternated with paramagnetic bimetallic layers.