In situ study on medium-range order evolution during the polyamorphous phase transition in a Pd-Ni-P nanostructured glass

•Bulk-sized nanostructured glasses that exceed millimeters have been prepared.•Short-range order structure stably remains before and after laser evaporation.•Medium-range order dominates the polyamorphous phase transitions induced by P and T.•Multiscale structures and properties can be tailored based on polyamorphism engineering.