A method is reported for fabricating complex 3D silver-coated polymeric microstructures. The approach is based on the creation of a crosslinked polymeric microscaffold via patterned multiphoton-initiated polymerization followed by surface-nucleated electroless deposition of silver. The conductivity and reflectivity of the resulting silver–polymer composites and the nanoscale morphology of the deposited silver are characterized. Sub-micrometer thick layers of silver can be controllably deposited onto surfaces, including those of 3D microporous forms without occluding the interior of the structure. The approach is general for silver coating crosslinked polymeric structures based on acrylate, methacrylate, and epoxide resins and provides a new path to complex 3D micrometer-scale devices with electronic, photonic, and electromechanical function.