Interest in three-dimensional (3D) metal photonic crystals (MPCs) has grown considerably given their potential applications in optics and photonics. Yet, experimental studies of such materials remain few because of the difficulties associated with fabricating 3D micron- and sub-micron-scale metallic structures. We report a route to MPCs based on metallization of 3D polymeric photonic crystals fabricated by multi-photon direct laser writing. Polymeric photonic crystals (PCs) having simple-cubic symmetry with periodicities varying from 1.6 to 3.2 μm were created using a cross-linkable acrylate pre-polymer. The resulting dielectric PCs were metallized by electroless deposition of silver. Analysis of the metallized structures in cross-section by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy shows that silver deposited conformally onto the entire micro-porous lattice. The dielectric and metallized PCs were characterized by Fourier transform infrared (FTIR) spectroscopy in the (001) direction. The polymer photonic crystals exhibit a stop band resulting in circa 60% reflectance centered at 3.2 to 6.4 μm, depending upon the lattice period, with a full-width at half-maximum (FWHM) of 500 nm. Interestingly, FTIR spectra of the metallized PCs show widened stop bands of nearly 6 μm FWHM, while the center wavelengths were red shifted and ranged from 6 to 7 μm. The appreciable broadening of the stop band due to the presence of the deposited silver is a result consistent with previously reported theoretical and experimental data for all-metallic 3D PCs. Thus, the approach described here appears suitable for fabricating 3D MPCs of many symmetries and basis sets and provides a path for integrating such structures with other micron-scale optical elements.