The removal of phosphorus from wastewaters is becoming very common, to meet water quality targets, and avoid environmental problems related to eutrophication. At the same time, agricultural application of P-rich sewage biosolids is diminishing for reasons of logistics and of public pressure. As a result P from wastewaters is ultimately disposed of in landfills. Over the long term, phosphate ore reserves will become depleted. Recycling of P from wastewaters may thus be a realistic prospect if scientific and technical issues can be resolved. At the centre of the scientific problems lie considerations about optimizing phosphate precipitation as Ca phosphates. A number of Ca phosphate minerals exist, although by far the most common of these is hydroxylapatite. Precipitation kinetic considerations, however, suggest that other Ca phosphates (such as brushite, octacalcium phosphate, whitlockite, monetite or amorphous Ca phosphate) may initially precipitate, and later recrystallize into the most stable hydroxylapatite. This article reviews the complex precipitation mineralogy, chemistry and kinetics of Ca phosphates.