A new process has been developed which allows electroless metal deposition on ordered arrays of resist structures with high aspect ratios (10–25 μm tall x 0.5–13 μm diameter). The fabricated structures have demonstrated ungated vacuum field emission at fields of 80–300 kV/cm in background pressures of 5 × 10-6 torr. The surface composition and Interface contamination relate directly to cathode performance. Cathode performance can be optimized by controlling the chemistry at these interfaces. X-ray Photoelectron Spectroscopy depth profiles, Scanning Auger Electron Spectroscopy, and Scanning Electron Microscopy have been used to characterize this system. These structures have potential vacuum microelectronics applications such as addressable electron emitters for flat panel displays.