Calcium phosphates offer outstanding biological adaptability. Thanks to their specific physico-chemical properties they are one of the most widely used materials in bone tissue engineering applications. The search for an innovative and economic strategy of synthesizing their different forms has been drawing considerable attention in the field. Herein, we report on a facile hydrothermal process in the presence of ethylenediamine tetraacetic acid and monoethanolamine to obtain various forms of calcium phosphates. The monoethanolamine served as an alkaline source and crystal growth modifier, while ethylenediamine tetraacetic acid was used to control the Ca2+ supersaturation level under high temperature and high pressure conditions. The obtained inorganic compounds were examined for their elemental composition, morphology, and structure using scanning electron microscopy, Raman spectroscopy, and powder x-ray diffraction. We were able to selectively synthesize monetite plate-like microcrystals as well as hydroxyapatite plates and nanofibers by simply varying the concentration of monoethanolamine.