The authors first report the three‐dimensional (3D) structured CeO2–PLA scaffold using a 3D printing methodology. The scaffold is prepared by decorating functional metal‐oxide nanoparticles onto the 3D‐printed polylactic acid (PLA) platform via an electrostatic interaction and is applied to the applications for photochemical degradation. As‐designed CeO2–PLA scaffold shows high photocatalytic degradation performance toward methyl orange under a light irradation. Furthermore, the CeO2–PLA scaffold shows reasonable degradation performance even after it is washed and reevaluated; this result demonstrates the benefit of 3D‐printed CeO2–PLA scaffold that it can be recycled several times without losing the catalysts.