The crystallization of piperazine in water as well as in systems loaded with CO2 has been studied for piperazine concentrations of 30–70 wt %, representing conditions relevant for CO2 capture. The use of a LabMax reactor system equipped with probes for in situ focused beam reflectance measurement (FBRM) and particle vision measurement (PVM) made it possible to determine solid–liquid transitions, crystal habit, and chord length distributions in these highly concentrated systems without disturbing the solid–liquid–gas equilibrium during crystallization. As shown by powder X-ray diffraction analysis, three phases including piperazine hemihydrate, piperazine hexahydrate, and anhydrous crystals were precipitated from the aqueous piperazine solutions at different concentrations and temperatures, as also supported by findings from FBRM and PVM. It was found that the metastable zone widths of the piperazine–H2O system were substantial even at the lower cooling rates, which could allow for a higher tolerance with respect to cooling prior to a new carbon dioxide absorption cycle. However, the eutectic composition exhibits a smaller metastable zone width than the other concentrations, which is believed to be caused by the precursor needle-shaped crystals, assisting the precipitation of the final product.