The microstructure of the melt-spun Cu60Hf30Ti10 and Cu50Hf40Ti10 alloys was investigated. The high-resolution transmission electron microscopy (HRTEM) image in the Cu60Hf30Ti10 alloy reveals the existence of nanoscale inhomogeneity, which appears to originate from nanocrystalline particles. The compositional segregation with a diameter of approximately 5 nm was detected, and its size agrees with the scale of nanocrystalline particle. Small-angle x-ray scattering measurement of the melt-spun Cu60Hf30Ti10 alloy also indicates the development of nanoscale inhomogeneity with the same size as that of nanocrystalline particles. It is found that the Cu element is enriched in and Hf element is rejected from the nanocrystalline particles. Since the melt-spun Cu50Hf40Ti10 alloy, which has a similar alloy composition to that of the glassy region of melt-spun Cu60Hf30Ti10 alloy, has a homogeneous glassy structure without fringe contrast in the HRTEM image, it is suggested that the excess of Cu causes the nanoscale inhomogeneity with crystalline structure in the rapidly quenched Cu–Hf–Ti alloys.