A number of novel nido-clusters of the type [Fe3(µ3-SbR)(µ3-Q)(CO)9] containing the heavier group 16 elements (Q = Se, Te) and Sb as group 15 element with attached functional groups (R = Cp*, (5-C5H4tBu)Fe(CO)2) have been obtained by the reaction of K2[Fe3(µ3-Q)(CO)9](Q = Se, Te) with RSbX2(X = Br, I). Furthermore, a first cluster [Fe3(µ3-BiFe(CO)2(5-C5H4tBu))(µ3-Se)(CO)9] containing a Bi/Se combination has also been synthesised in a similar manner. The novel complexes were comprehensively characterised by various spectroscopic methods as well as by single crystal X-ray diffraction methods.