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Mo-Re alloys have excellent mechanical and processing properties due to their high-temperature resistance, corrosion resistance, and plasticity. To further understand the microstructure and room temperature tensile properties of rolled Mo-14%Re alloy, the microstructure and fracture morphology of the Mo-14%Re alloy were investigated by scanning electron microscopy (SEM) and high-resolution electron backscatter diffraction (EBSD). Channel 5 software was used to analyze the microstructure evolution of rolled Mo-14%Re alloy at different annealing temperatures. With the increase in annealing temperature, the Schmidt factor of the Mo matrix phase and ReO₃ phase decreases gradually. The texture intensity increases rapidly, and the crystal orientation intensity of the polarography increases from 6.51 to 10.18. The initial recrystallization of the rolled Mo-14%Re alloy occurs at 1100 °C, at which the uniform precipitation of the earth-rich ReO₃ phase in the alloy leads to uniform stress distribution during tensile process, the grains of Mo matrix phase and ReO₃ phase show obvious ＜101＞ crystal orientation and ＜111＞ crystal orientation, and the grain boundaries of ReO₃ phase are mainly high-angle grain boundaries, which makes the elongation after fracture reach the maximum of 33.5%. The tensile fracture has the highest number of dimples and the largest size. Besides, the formation, aggregation, growth, and crack propagation of micropores during fracture were studied.