Nb–silicide in situ composites have great potential for high-temperature turbine applications. Nb–silicide composites consist of a ductile Nb-based solid solution together with high-strength silicides, such as Nb5Si3 and Nb3Si. With the appropriate addition of alloying elements, such as Ti, Hf, Cr, and Al, it is possible to achieve a promising balance of room-temperature fracture toughness, high-temperature creep performance, and oxidation resistance. In Nb–silicide composites generated from metal-rich binary Nb-Si alloys, Nb3Si is unstable and experiences eutectoid decomposition to Nb and Nb5Si3. At high Ti concentrations, Nb3Si is stabilized to room temperature, and the eutectoid decomposition is suppressed. However, the effect of both Ti and Hf additions in quaternary alloys has not been investigated previously. The present article describes the discovery of a low-temperature eutectoid phase transformation during which (Nb)3Si decomposes into (Nb) and (Nb)5Si3, where the (Nb)5Si3 possesses the hP16 crystal structure, as opposed to the tI32 crystal structure observed in binary Nb5Si3. The Ti and Hf concentrations were adjusted over the ranges of 21 to 33 (at.%) and 7.5 to 33 (at.%) to understand the effect of bulk composition on the phases present and the eutectoid phase transformation.