Because of various excellent properties of low density, high specific strength and stiffness, high modulus, good thermal stability and corrosion-resistant, beryllium-aluminum (Be-Al) alloys have shown great potential to be used in nuclear industries. However, Be-Al alloys suffer from the bottlenecks of low solubility between Be and Al and the lack of effective technology for fabricating large-sized products. Herein, based on Sc and Zr addition, Be-Al-Sc-Zr alloys are successfully fabricated by conducting the electron beam welding (EBW) technology, and the effect of Sc and Zr addition on microstructure, mechanical property and fracture behavior of Be-Al-Sc-Zr alloys is studied. Microstructural characterizations show that both the EBWed Be-Al and Be-Al-Sc-Zr alloys exhibit two distinct zones of substrate zone (SZ) and fusion zone (FZ). Compared to grain size of the SZ and FZ in Be-Al alloys, grain sizes of these two zones in Be-Al-Sc-Zr alloys are significantly refined, thus leading to ultimate tensile strength (UTS) of the Be-Al-Sc-Zr alloys (~176MPa) approximately 150% higher than that of the Be-Al alloys (~118MPa). Besides, a newly generated third phase (TP), which is confirmed as Be13(Scx, Zr1-x), forms within Al phase in both SZ and FZ of the Be-Al-Sc-Zr alloys. Different from fracture behavior of Be-Al alloys that preferentially fractures within Al phase or near the Be/Al interface, fracture of the Be-Al-Sc-Zr alloys is prone to occur within Be phase. As revealed by the calculation results of finite element method (FEM), the underlying mechanism for different fracture behaviors mainly ascribes to that the reinforcement of the Al phase and the existence of the newly formed TP can greatly increases the internal stress and even causes stress concentration within Be phase of the Be-Al-Sc-Zr alloys. The present findings may provide more insights to the micro-alloying and deformation mechanism of Be-Al alloys that with enhanced mechanical properties.