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The compression of Zr44.4Nb7 Cu13.5Ni10.8Be24.3 bulk metallic glass (BMG) is investigated at room temperature up to 39 Gpa using in situ high-pressure energy dispersive x-ray diffraction with a synchrotron radiation source.The equation of state of the BMG is obtained by the calculation of the radial distribution function. Pressureinduced structural relaxation is exhibited. It is found that below about 6 Gpa, the existence of excess free volume contributes to the rapid structural relaxation, which gives rise to rapid volumetric change, and the structural relaxation results in structural stiffness under higher pressure.