//Nbss and α-Nb5Si3 phases were detected. Meanwhile, Nb2C was observed, and the crystal forms of Nb5Si3 changed in the C-doped composites. Furthermore, micron-sized and nano-sized Nb2C particles were found in the Nbss layer. The orientation relationship of Nb2C phase and the surrounding Nbss was [001]Nbss//[010]Nb2C, (200) Nbss//(101) Nb2C. Additionally, with the addition of C, the compressive strength of the composites, at 1400 °C, and the fracture toughness increased from 310 MPa and 11.9 MPa·m1/2 to 330 MPa and 14.2 MPa·m1/2, respectively; the addition of C mainly resulted in solid solution strengthening.