Direct writing using a focused electron beam allows for fabricating truly three-dimensional structures of sub-wavelength dimensions in the visible spectral regime. The resulting sophisticated geometries are perfectly suited for studying light–matter interaction at the nanoscale. Their overall optical response will strongly depend not only on geometry but also on the optical properties of the deposited material. In the case of the typically used metal–organic precursors, the deposits show a substructure of metallic nanocrystals embedded in a carbonaceous matrix. Since gold-containing precursor media are especially interesting for optical applications, we experimentally determine the effective permittivity of such an effective material. Our experiment is based on spectroscopic measurements of planar deposits. The retrieved permittivity shows a systematic dependence on the gold particle density and cannot be sufficiently described using the common Maxwell–Garnett approach for effective medium.