This review paper on amorphous calcium phosphates (ACPs) provides an update on several aspects of these compounds which have led to many studies and some controversy since the 1970s, particularly because of the lack of irrefutable proof of the occurrence of an ACP phase in mineralised tissues of vertebrates. The various synthesis routes of ACPs with different compositions are reported and the techniques used to characterise this phase are reviewed. We focus on the various physico-chemical properties of ACPs, especially the reactivity in aqueous media, which have been exploited to prepare bioactive bone substitutes, particularly in the form of coatings and cements for orthopaedic applications and composites for dental applications