A positron annihilation study of free volumes was performed on Cu-Zr and Al-Sm alloys in the course of repeated cold rolling (RCR) in order to contribute to the microscopic understanding of the complex processes of solid-state amorphization and nanocrystallization. In addition to positron lifetime spectroscopy, which yields information on the size of free volumes, twodimensional Doppler broadening technique was applied in order to study the local chemical environment of free volumes on an atomistic scale. Both in Cu60Zr40 and Al92Sm8 a characteristic variation of the chemical environment of free volumes with the number of folding and rolling (F&R) cycles could be observed. In the first (Al-Sm) and intermediate state (Cu-Zr) of F&R, free volumes with an enhanced amount of Sm or Zr content in the local environment occur, indicating interfacial segregation or the formation of solute-vacancy complexes. Upon further F&R cycling, a complete (Cu-Zr) or partially amorphous structure (Al-Sm) is obtained with the free volumes exhibiting a chemical environment characteristic of the average chemical composition. In contrast to melt-spun or ball-milled amorphous alloys, free volumes of the size of a few missing atoms are found in amorphous alloys prepared by RCR presumably due to strong athermal conditions of F&R cycling.