In this paper, Mo14Re powders were prepared by high-energy ball milling (HEBM) and spray-drying-hydrogen reduction (SPHR), respectively. Then, the Mo14Re alloys were obtained by spark plasma sintering (SPS). The phase structure, micro-structure, element distribution, and grain size were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron backscatter diffraction (EBSD), respectively. The deformation mechanisms of Mo14Re alloy under room temperature tension and compression were discussed. The XRD results indicated that the (101)-spacing of the Mo14Re-SPHR is smaller than that of the Mo14Re-HEBM. The EDS results show that the segregation of Re is observed at the grain boundary of the Mo14Re-HEBM, while elements distribution is uniform in the Mo14Re-SPHR alloy. The room temperature compression results showed that the compressive yield strength of the Mo14Re-SPHR is 679.11 MPa, higher than that of the Mo14Re-HEBM (602.71 MPa). EBSD results showed that when the compression deformation is larger than 5.0%, the proportion of grains with {123}<111>as the main slip system in Mo14Re-SPHR increased, while the proportion of grains with {110}<111>and {112}<111>as the main slip systems decreased. The change trend of the three slip systems in Mo14Re-HEBM was opposite to that in Mo14Re-SPHR, resulting in a higher strain hardening rate of Mo14Re-HEBM than Mo14Re-SPHR.Room temperature tensile results show that Mo14Re-SPHR exhibits better plasticity and toughness.