3D-printed titanium (Ti) materials have attracted much attention in the field of bone tissue repair. However, the combination strength of traditional alloy materials with bone tissue is lower, and the elastic modulus is higher than that of natural bone tissue, which makes the titanium alloy susceptible to stress shielding phenomena after implantation. Therefore, it is urgent to find better surface modification technology. In this study, the physical and chemical properties, toxicity, and proliferation of adipose stem cells of composite graphene-coated titanium alloy (Gr–Ti) were investigated using 3D-printed titanium alloy as a material model. Physical and chemical property tests confirmed that 3D printing could produce porous titanium alloy materials; the compressive strength and elastic modulus of the titanium alloy scaffolds were 91 ± 3 MPa and 3.1 ± 0.4 GPa, matching the elastic modulus of normal bone tissue. The surface characterization shows that graphene can be coated on titanium alloy by a micro-arc oxidation process, which significantly improves the surface roughness of titanium alloy. The roughness factor (Ra) of the Ti stent was 4.95 ± 1.12 μm, while the Ra of the Gr–Ti stent was 6.37 ± 0.72 μm. After the adipose stem cells were co-cultured with the scaffold for 4 h and 24 h, it was found that the Gr–Ti scaffold could better promote the early cell adhesion. CCK-8 tests showed that the number of ADSCs on the G–Ti scaffold was significantly higher than that on the Ti scaffold (p < 0.01). The relative growth rate (RGR) of ADSCs in Gr–Ti was grade 0–1 (non-toxic). In the in vivo experiment of repairing a critical bone defect of a rabbit mandible, the bone volume fraction in the Gr–Ti group increased to 49.42 ± 3.28%, which was much higher than that in the Ti group (39.76 ± 3.62%) (p < 0.05). In conclusion, the porous graphene–titanium alloy promotes the proliferation and adhesion of adipose stem cells with multidirectional differentiation potential, which has great potential for the application of bone tissue engineering in repairing bone defects in the future.