Surface overcuring in volumetric additive manufacturing (VAM) occurs when material, process, and hardware parameters are not properly coordinated, leading to unintended polymerization near the vat boundary and impaired printability. Here, we develop a generalized theoretical model to predict the spatial light-dose distribution within rotating ink and to investigate the effects of key physical parameters, including projection beam size, vat dimensions, occlusion size, and material absorbance, on the onset of surface overcuring. The results show that this defect can be effectively suppressed through the synergistic regulation of these parameters. Specifically, lower material absorbance, smaller vat diameters, and narrower projection beams concentrate higher light energy in the central region of the vat while reducing energy deposition near the sidewalls, thereby promoting earlier solidification in the target region and preventing surface overcuring. Based on this model, a printing process window for suppressing surface overcuring is established as a quantitative guide for the design and fabrication of complex structures by VAM. The practical utility of this process window is further demonstrated through the successful fabrication of functional pH-responsive single- and multi-material drug delivery systems with controllable drug-release profiles. Overall, this study expands the printable design space of VAM for complex 3D structures and provides a practical framework for more advanced applications.