A method of manufacturing photonic band gap structures operable in the optical spectrum has been presented. The method comprises the steps of filling a plurality of grooves of an elastomeric mold with a UV curable first polymer, each groove in parallel with each other and partially curing the first polymer. A second polymer is coated on the first polymer. A substrate or a multi-layer polymer structure is placed on the filled mold and the resulting structure is exposed to UV light (i.e., is UV cured). The mold is peeled away from the first and second polymers such that a layer of polymer rods is formed on the substrate/multi-layer polymer structure. The process is repeated until a desired number of layers have been formed. The multi-layer structure can be used to create ceramic and metallic photonic band gaps by infiltration, electro-deposition, and/or metal coating.