Calcium phosphates form a vast family of biominerals, which have attracted much attention in fields like biology, medicine, and materials science, to name a few. Solid state Nuclear Magnetic Resonance (NMR) is one of the few techniques capable of providing information about their structure at the atomic level. Here, examples of recent advances of solid state NMR techniques are given to demonstrate their suitability to characterize in detail synthetic and biological calcium phosphates. Examples of high-resolution 31P, 1H (and 17O), solid state NMR experiments of a 17O-enriched monocalcium phosphate monohydrate-monetite mixture and of a mouse tooth are presented. In both cases, the advantage of performing fast Magic Angle Spinning NMR experiments at high magnetic fields is emphasized, notably because it allows very small volumes of sample to be analyzed.