This work discovers that Cu 2 O nanocrystals with controllable structures can be synthesized on surfaces of nanoporous Cu and amorphous ribbons by free dealloying of Cu-based amorphous alloys in acidic solutions. Technological parameters, such as the acid, acid concentration, and dealloying time strongly influence the crystal size, structure and morphology of Cu 2 O. Cu 2 O nanocubes are fabricated on surfaces of nanoporous Cu in the hydrofluoric acid treated alloy, while various Cu 2 O particles are tailored on surfaces of amorphous alloys immersed in hydrochloric acid for different time. The increasing dealloying time and adsorbed oxygen improve the growth rates along the 1 0 0 direction of Cu 2 O crystals relative to that of the 1 1 1 direction, which is the key to change the shapes of Cu 2 O crystals. The understanding of morphology evolution of Cu 2 O nanocrystals in this work is helpful in tailoring Cu 2 O particles with designable shapes and controllable properties in application fields.