In this study, phosphogypsum waste collected from a factory dump in Kedainiai, Lithuania, was used for the first time as a starting material in the dissolution–precipitation synthesis of high-quality bioceramic calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂; CHA). The CHA powders were synthesized using the dissolution–precipitation method, employing phosphogypsum in four different conditions: untreated, dried at 100 °C, dried at 150 °C, and annealed at 1000 °C. Various phosphorus sources were used in the CHA synthesis process: Na₂HPO₄; a mixture of Na₂HPO₄ and NaH₂PO₄; or a combination of Na₂HPO₄, NaH₂PO₄, and NaHCO₃. These mixtures were allowed to react at 80 °C for 48 h, 96 h, 144 h, and 192 h. X-ray diffraction (XRD) analysis revealed slight variations in the synthesized products depending on the specific starting materials used. Fourier transform infrared spectroscopy (FTIR) was conducted to confirm the structural characteristics of the synthesized CHA samples. The surface microstructure of the synthesized CHA samples differed notably from that of the raw phosphogypsum. All synthesized CHA samples exhibited Type IV nitrogen adsorption–desorption isotherms with H3-type hysteresis loops, indicating the presence of mesoporous structures, typically associated with slit-like pores or aggregates of plate-like particles. To the best of our knowledge, an almost monophasic CHA has been fabricated from phosphogypsum waste for the first time using a newly developed dissolution–precipitation synthesis method. A key challenge in the high-end market is the development of alternative synthesis technologies that are not only more environmentally friendly but also highly efficient. These findings demonstrate that phosphogypsum is a viable and sustainable raw material for CHA synthesis, with promising applications in the medical field, including the production of artificial bone implants.