Purpose: To study the accuracy with which proton stopping power ratio (SPR) can be determined with dual-energy computed tomography (DECT) for small structures and bone-tissue-air interfaces like those found in the head or in the neck. Methods: Hollow cylindrical polylactic acid (PLA) plugs (3 cm diameter, 5 cm height) were 3D printed containing either one or three septa with thicknesses t septa = 0.8, 1.6, 3.2, and 6.4 mm running along the length of the plug. The cylinders were inserted individually into a tissue-equivalent head phantom (16 cm diameter, 5 cm height). First, DECT scans were obtained using a Siemens SOMATOM Definition Edge CT scanner. Effective atomic number (Z eff ) and electron density (q e ) images were reconstructed from the DECT to produce SPR-CT images of each plug. Second, independent elemental composition analysis of the PLA plastic was used to determine the Z eff and q e for calculating the theoretical SPR (SPR-TH) using the Bethe-Bloch equation. Finally, for each plug, a direct measurement of SPR (SPR-DM) was obtained in a clinical proton beam. The values of SPR-CT, SPR-TH, and SPR-DM were compared. Results: The SPR-CT for PLA agreed with SPR-DM for t septa ≥ 3 mm (for CT slice thicknesses of 0.5, 1.0, and 3.0 mm). The density of PLA was found to decrease with thickness when t septa < 3 mm. As t septa (and density) decreased, the SPR-CT values also decreased, in good agreement with SPR-DM and SPR-TH. Conclusion: Overall, the DECT-based SPR-CT was within 3% of SPR-TH and SPR-DM in the highdensity gradient regions of the 3D-printed plugs for septa greater than~3mm in thickness.