We have previously described the development of a microstereolithography (µSL) system using a Digital Micromirror Device (DMD) for dynamic pattern generation and an ultraviolet (UV) lamp filtered at 365 nm for crosslinking a photoreactive polymer solution. The µSL system was designed with x–y resolution of approximately 2 µm and a vertical (z) resolution of approximately 1 µm (with practical build limitations on vertical resolution of approximately 30 µm due to limitations on controlling UV penetration in z). The developed µSL system is capable of producing real three-dimensional (3D) microstructures, which can be employed in applications such as microfluidics, tissue engineering, and various functional microsystems. Many benefits will potentially be derived from producing multiple material microstructures in µSL, and one particular application area of interest is in producing multi-material microscaffolds for tissue engineering. In the present work, a method for multi-material µSL fabrication was developed using a syringe pump system to add a material to a small, removable vat designed specifically for the multi-material µSL system. Multi-material fabrication was accomplished using a material changeover process that included manually removing the vat, draining the current material, rinsing the vat, returning the vat to the system, and finally dispensing a prescribed volume in the vat using the syringe pump. Layer thicknesses of approximately 30 µm were achieved using this process. To demonstrate this system, several multi-material microstructures were produced to highlight the capability of this promising technology for fabricating 3D functional, multi-material microstructures with spatial control over placement of both material and structure.