The effect of strontium (Sr) addition (0.2 at.%) on the microstructure and mechanical properties of Nb-12Si-22Ti alloys were studied. Microstructure of the alloys was observed by scanning electron microscope, and their phase compositions were analyzed with X-ray diffraction and Electro-Probe Microanalyzer. The room temperature fracture toughness was measured. The results indicated that the phases of Nbss and Nb3Si were presented in Nb-12Si-22Ti alloys. However, with the Al and Sr addition, the alloys were composed of Nbss and β-Nb5Si3. Compared with the Nb-12Si-22Ti alloys, the value of room temperature fracture toughness increased about 46% and 73% with the addition of Al and Sr alloy, respectively. The relationship between the microstructure and the mechanical properties was discussed.