Provided are methods of forming a printed circuit board having optical functionality. The methods involve: (a) providing a first, printed circuit board substrate; (b) forming an optical waveguide structure comprising a clad and a core structure on a second substrate separate from the printed circuit board substrate, wherein the optical waveguide structure comprises a silicon-containing material; (c) separating the optical waveguide structure from the second substrate; and (d) affixing the optical waveguide structure to the printed circuit board substrate. The invention has particular applicability in the electronics and optoelectronics industries for the formation of hybrid printed circuit boards.