Electron microscopy of the composite-forming alloys Ti60Cu14Ni12Sn4Nb10 and Ti60Cu14Ni12Sn4Ta10, shows that for both alloys, the microstructure consists of an array of micron-scale dendrites surrounded by a nanoscale binary eutectic. In the Ta-containing alloy, one of the eutectic phases has been identified as having a bcc crystal structure similar to that of the dendrites. In the Nb-containing alloy, one of the eutectic phases has been found to have a similar composition to that of the dendrites. Further detailed structural and compositional characterization is needed in order to understand the solidification behaviour of such materials. This knowledge may then be used to improve the casting conditions and subsequent mechanical properties of the materials.