We report on the synthesis and fabrication of novel polymer/organic materials for application for what we call optical printed circuit board (O-PCB) for VLSI photonic circuit (VLSI-PIC). We synthesize copolymers containing cross-linkable pendant groups suitable for embossing and novel device fabrication. We also synthesize organic-inorganic hybrid materials of low optical absorption, good adhesion, low dielectric constant, high dielectric strength, high thermal stability, excellent photo-patterning possibility and variability of refractive index. Steps of synthesis and fabrication of these materials are described along with their optical, material, and performance characteristics. O-PCB and VLSI photonic circuit design and fabrication processes are also presented.