Disclosed is a printed circuit board with opto-via holes for transmitting an optical signal to an optical waveguide in the PCB, and a process of forming the opto-via holes. The process comprises forming a plurality of via holes on a plurality of copper clad laminates using a drill, plating an inner wall of each via hole, exposing and etching the plated portions of an upper and lower side of each copper clad laminate to form a circuit pattern on the upper and lower side of the copper clad laminate, layering the patterned copper clad laminates on each other using an insulating resin adhesive, and removing the insulating resin adhesive in the predetermined via holes to form opto-via holes. Therefore, the process is advantageous in that the optical signal is stably transmitted to the optical waveguide in the PCB without damage to the optical waveguide directly exposed to an external environment, and the optical waveguide suitable to physical properties of the material constituting the PCB is easily inserted between the inner layer and the outer layer.