We demonstrate a new technique for selectively growing gold nanoparticles on a patterned three-dimensional (3D) polymer microstructure. The technique integrates 3D direct writing of heterogeneous microstructures with nanoparticle synthesis. A digital micromirror device is employed as a dynamic mask in the digital projection photopolymerization process to build the heterogeneous microstructure layer by layer. An amine-bearing polyelectrolyte, branched poly(ethylenimine), is selectively attached to the microstructure and acts as both a reducing and a protective agent in the nanoparticle synthesis. Scanning electron microscopy, energy dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy are utilized to analyze the microstructure and the 3D selectivity of the nanoparticle growth.