Poly(lactic acid) (PLA) is currently the most widely used material in 3D printing. PLA has good mechanical properties, chemical stability, and biodegradability, but its surface is hydrophobic and cannot be effectively used. The growth metabolism of attachments, how to increase the strength of PLA with high brittleness, and 3D printing of PLA materials for the biomedical field have always been a topic of research by scientists. This experiment used fused filament fabrication (FFF) to prepare structures. First, the 3D-printed polymer surfaces were treated with an atmospheric-pressure plasma jet (APPJ) to make the surface hydrophilic and increase the number of polar functional groups on the surface. Then, UV photo-grafting polymerization of 2-hydroxyethyl methacrylate (HEMA), poly(ethylene glycol) methacrylate (PEGMA), and hydroxyapatite (HAp) was applied onto the 3D-printed polymer surfaces. The experimental results of the water contact angle for the wettability test show that APPJ-treated and UV-grafted composite hydrogels become hydrophilic to activate the 3D-printed polymer surface successfully. For the in vitro study, the effect of APPJ treatment and composite hydrogel on the viability of osteoblast-like MG63 cells was examined using the Alamar Blue cell viability assay, indicating that biocompatibility has been improved in this study. This method is expected to have potential in the application of bone scaffolds in the future.