Ultramicrotoming has been employed to prepare thin cross-sections of Ni-P alloys electrodeposited on to a copper substrate. The sections, as thin as 10nm or even less, can be prepared readily with negligible damage to the alloys. Subsequent examination of the ultramicrotomed sections in an analytical transmission electron microscope has revealed that Ni-P alloys of low P content consist of fine layers of different composition and crystallinity. High-resolution transmission electron microscopy of ultramicrotomed sections has also revealed the presence of ordered regions, a few nanometres in size, in the Ni77P23alloy which has been thought previously to be amorphous.