The mechanism of pore evolution in vacuum electron beam joints of Mo-14Re alloy has been thoroughly investigated. Microscopic characterization methods, including Optical Microscopy (OM) and Scanning Electron Microscopy (SEM), were employed to explore the evolution mechanism of pore defects at different locations. Weld defects were further characterized using Energy Dispersive Spectroscopy (EDS) and Transmission Electron Microscopy (TEM), providing insights into their formation mechanisms. The findings reveal that pores along grain boundaries are the result of MoO and CO bubble aggregation. Non-equilibrium solidification of the melt triggers chemical reactions, transforming MoO and CO bubbles into MoO3 and C, with lower melting points. MoO3 and C persist in the pores, leading to the formation of grain boundary gas hole defects. On the other hand, intragranular pore defects stem from an abundance of pores within the matrix material. Upon entry of gas from these pores into the molten pool, its escape is impeded due to the intense influence of the molten pool. After the molten pool completes the cooling and solidification process, the gas remains within the crystal, resulting in intragranular pore defects.