Element distribution of the bulk amorphous Zr41Ti14Cu12.5Ni10Be22.5 alloy and of the zone around the structural free volume in the undercooled liquid region was investigated by X-ray diffraction (XRD) and positron annihilation techniques(PAT)-Doppler broadening spectrum. Results show that the structural free volumes in the initially prepared Zr41Ti14Cu12.5Ni10Be22.5 alloy were mainly surrounded by Zr atoms. After the alloy was annealed at 400 ℃ in the undercooled liquid region, both atoms Ti and Be together with Zr were detected to surround the structural free volumes.