The Si matrix phase of directionally solidified Si‐TaSi2composite structures has been characterized by deep level capacitance transient spectroscopy, using the grown‐in metal‐semiconductor junctions. The Si is found to be of high quality. No electrically active Ta was detected with a minimum experimental sensitivity of ∼6×1011cm−3. Some samples exhibited one of two defect states having electron emission activation energies of 0.36 and 0.65 eV. These states appear to be associated with dislocations.