Guided Bone Regeneration (GBR) is one of the key components of contemporary dental treatments for the restoration of alveolar bone before the placement of an implant. In the past few years, the advent of patient-specific, 3D-printed polycaprolactone (PCL) scaffolds has made a remarkable advance in this field; these custom-made scaffolds now have the potential to significantly enhance the outcome of bone regeneration by conforming to the anatomical needs of the patient. This narrative review describes the existing 3D-printed PCL membranes and scaffolds used in GBR, covering topics such as design and fabrication techniques, biological compatibility, mechanical properties, and degradation characteristics. A comparison is made with standard collagen membranes, noting the advantages and potential shortcomings of this technology. A mixed methodology combining clinical case evaluations, in vitro studies, in vivo animal studies, and an extensive literature review was designed. The PCL scaffold was manufactured using additive technology, aminolyzed with gelatin, and evaluated concerning volumetric and histological outcomes in a staged ridge augmentation procedure. The scaffold shown excellent biocompatibility, structural strength, and osteoconductivity after surface modification. An impressive volumetric increase of 108.4% in bone formation was recorded, with favorable histological integration achieved without any significant inflammation or surgical complications. These findings highlight the potential of custom 3D-printed PCL scaffolds as a practical and advanced alternative for GBR. Tailoring to the unique anatomy of each patient enhances regenerative outcomes, thus sagging towards an improved predictability of the surgical procedures. Meanwhile, other challenges still lie ahead, like relatively slow biodegradation of the PCL, regulatory issues, and high production cost, all of which should be critically examined and eliminated to guarantee greater clinical acceptance.