Hydroxyapatite (HA), the main inorganic bone component, is the most widely researched bioceramic for bone repair. This paper presents a comprehensive review of recent advancements in HA synthesis methods and their integration into additive manufacturing (AM) processes. Synthesis methodologies discussed include wet, dry, and biomimetic routes, emphasizing their impact on tailoring the physicochemical properties of HA for biomedical applications. The incorporation of dopants and additives during synthesis is explored for optimizing the mechanical, biological, and osteogenic characteristics of HA-based materials. Moreover, the evolution of AM technologies from conventional 3D printing to advanced 4D and 5D printing is detailed, covering material selection, process parameters, and post-processing strategies vital for fabricating intricate, patient-specific scaffolds, implants, and drug delivery systems utilizing HA. The review underscores the importance of achieving precise control over microstructure and porosity to mimic native tissue architectures accurately. Furthermore, emerging applications of HA-based constructs in tissue engineering, regenerative medicine, drug delivery, and orthopedic implants are discussed, highlighting their potential to address critical clinical needs. Despite the glimmer of hope provided by the advent and progress of such AM capabilities, several aspects need to be addressed to develop efficient HA-based bone substitutes, which are explored in detail in this review.