Woodpile photonic crystals are amongst the preferred candidates for the next generation of photonics components. However, the photocurable resists used to produce them still lack the optical properties (high-n, non-linearity) suitable for photonics applications. A chemical bath deposition protocol has been adapted to deposit high-n/non-linear chalcogenide CdS on the surface of Ormocer® woodpiles. The deposition parameters have been adjusted to obtain heterogeneous growth of CdS layers on the Ormocer® surface. The layers shift the photonic band-gap and increase its amplitude by more than 15%. Software simulation confirmed that the woodpile effective refractive index underwent an excess of 30% increase.