Nb-base in-situ composites, which have the base composition of Nb-18Si-5Mo-5Hf, have been investigated in microstructure, hardness (Hv*), Young’s modulus (E), tensile properties and fracture behavior. The microstructures of all composites examined consist of NbSS matrix and Nb5Si3 secondary phases. No secondary phase such as Nb2C appeared. The crystal structure of Nb5Si3 is Mn5Si3-type when C replaces 2mol%-Nb, though typical structures of a (Cr5B3-type) and b (W5Si3-type) as in the base composition when W replaces. W addition is effective in increasing Hv* and E of both phases as expected. However, C alloying is somewhat beneficial only in Nb5Si3 with a noticeable negative effect in NbSS. Furthermore, the composite exhibits the highest strength at 1473 K, while the base composite exhibits the highest at room temperature. The fracture behavior is independent of the compositions and it is controlled by cleavage fractures of Nb5Si3, decohesion of NbSS/Nb5Si3 interface and ductile rupture of NbSS depending on the testing temperatures.