Dense Nb/Nb5Si3composites were fabricated via spark plasma sintering technology using Nb, Si, and Al elemental powders as raw materials. The microstructures of the synthesised composites were analysed through scanning electron microscopy, X-ray diffraction, and electron probe microanalysis. The results show that the composites consisted of residual Nb particle phase and Nb5Si3phase. The microstructure of the Nb/ Nb5Si3in situ composites was evidently affected by Al addition, which prompted the formation of the Al3Nb10Si3phase. The oxidation resistance of the Nb/Nb5Si3in situ composites significantly improved with the increase in Al addition. Pesting oxidation behaviour was exhibited at 800°C by the Nb-20Si composites when exposed to air for 4h. This pest oxidation behaviour is not exhibited by the Nb-20Si-10Al and Nb-20Si-15Al composites after exposure to air for ~10h. The composite exhibits the best oxidation resistance at 15at% Al.