In this dissertation, we demonstrate the fabrication of high fidelity 3D photonic crystal through polymer template fabrication, backfilling and template removal to obtain high index inversed inorganic photonic crystals (PCs). Along the line, we study the photoresist chemistry to minimize the shrinkage, backfilling strategies for complete infiltration, and template removal at high and low temperatures to minimize crack-formation. Using multibeam interference lithography (MBIL), we fabricate diamond-like photonic structures from commercially available photoresist, SU-8, epoxy functionalized polyhedral oligomeric silsesquioxane (POSS), and narrowly distributed poly(glycidyl methacrylate)s (PGMA). The 3D structure from PGMA shows the lowest shrinkage in the [111] direction, 18%, compared to those fabricated from the SU-8 (41%) and POSS (48%) materials under the same conditions. To fabricate a photonic crystal with large and complete photonic bandgap, it often requires backfilling of high index inorganic materials into a 3D polymer template. We have studied different backfilling methods to create three different types of high index, inorganic 3D photonic crystals. Using SU-8 structures as templates, we systematically study the electrodeposition technique to create inversed 3D titania crystals. We find that 3D SU-8 template is completely infiltrated with titania sol-gel through a two-stage process: a conformal coating of a thin layer of films occurs at the early electrodeposition stage (< 60 min), followed by bottom-up deposition. After calcination at 500 oC to remove the polymer template, inversed 3D titania crystals are obtained. The optical properties of the 3D photonic crystals characterized at various processing steps matches with the simulated photonic bandgaps (PBGs) and the SEM observation, further supporting the complete filling by the wet chemistry. Since both PGMA and SU-8 decompose at a temperature above 400 oC, leading to the formation of defects and cracks, a highly thermal and mechanical stable template is desired for PC fabrication. We fabricate the 3D POSS structures by MBIL, which can be converted to crack-free silica-like templates over the entire sample area (~5 mm in diameter) by either thermal treatment in Ar at 500 oC or O2 plasma, and the porosity can be conveniently controlled by O2 plasma power and time. Since POSS derivatives are soluble in HF aqueous solutions, we successfully replicate the 3D porous structures into polymers, such as PGMA and poly(dimethyl siloxane) (PDMS). We note that all the fabrication processes are conducted at room temperature, including template fabrication, infiltration and removal. Further, using 3D POSS structures as templates, here, we demonstrate the synthesis of 3D photonic crystals from silicon carbide and boron carbide, respectively, which are thermally stable above 1100 oC in Ar. These non-oxide ceramic photonic crystals are potentially useful as ultrahigh temperature thermal barrier coatings that provide thermal protection for metallic components.