Recurrent acidic exposure in patients with gastroesophageal reflux disease (GERD) accelerates the degradation of provisional restorative materials, whereas approaches to enhance the acid resistance of 3D-printed restorations remain inadequately characterized. This study aimed to evaluate the effect of graphene oxide (GO) incorporation on the surface properties and acid resistance of 3D-printed provisional restorative materials under simulated gastroesophageal reflux conditions. GO was synthesized using the Hummers’ method and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. XRD analysis demonstrated a pronounced shift in the characteristic peak (2θ) from 26° to 12°, consistent with an expansion of interlayer spacing after oxidation. FTIR confirmed the presence of oxygen-containing functional groups (hydroxyl, carbonyl, and epoxy), while Raman spectroscopy identified the characteristic D and G bands, confirming successful GO synthesis. Temporary Crown & Bridge resin (TC100) was modified with GO at six concentrations (0, 0.025, 0.05, 0.1, 0.5, and 1.0 wt %) using a planetary ball milling technique. Standardized 3D-printed specimens (n = 24 per group) were fabricated. Surface roughness and Vickers microhardness were measured before and after 45 h of immersion in simulated gastric acid (pH 2). Data were analyzed using one-way ANOVA and paired t-tests (α = 0.05). After acid exposure, the control group (0 wt % GO) exhibited significant surface deterioration, showing the highest surface roughness and a marked reduction in hardness (p < 0.05). Conversely, GO-modified groups demonstrated a concentration-dependent improvement in resistance to acid-induced degradation. The 0.5 wt % GO group showed the most favorable performance, maintaining both surface roughness and hardness with no significant difference from baseline values (p > 0.05). These findings indicate that GO incorporation enhances the surface integrity and acid resistance of 3D-printed provisional resins, with 0.5 wt % identified as the optimal concentration for minimizing acid-induced surface deterioration.