Nanoscale structural change in (Fe0.5Co0.5)72B20Si4Nb4 bulk glassy alloy on annealing has been investigated using transmission electron microscopy. On annealing at temperatures above 773K, electron diffraction intensity analysis showed a clear structure change for a Cr23C6-type local atomic ordering. The local structure formation of Cr23C6-type nanophase was confirmed by nanobeam electron diffraction. A development process of dense precipitates of the Cr23C6-type nanophase was further studied by high-resolution electron microscopy. It was found that the formation of the highly-dense nanoprecipitates provides an increase in Vickers hardness.