The crystallographic structures and surface morphologies of Fe-P binary alloy films electrodeposited at different bath concentrations and different electrodeposition conditions have been studied in detail by means of XRD, HRTEM and SEM. The crystallization sequences of deposited films under the heat-treatment were analyzed with the help of XRD. The crystallographic structures of Fe-P deposited films were also compared with the Fe-P thermal equilibrium phase diagram. The results indicate that the crystallographic structures of Fe-P deposited films gradually change from crystalline to amorphous phase with increasing P content in the deposited films. The deposited film exists as -Fe supersaturated solid solution when the P compositions in deposited film are below 20.5 at%, whereas it exists as a homogenous amorphous phase when the P compositions in the deposited films are from 22.2 at% to 30.1 at%. Accordingly, the composition of boundary between the crystalline and homogenous amorphous regions can be determined at about 21.4 at% P content.