It has been just over two decades since John and Yablonovitch theoretically predicted the existence of a complete photonic band gap in 3D silicon photonic crystals, a range of wavelengths for which light is forbidden to propagate in all three spatial dimensions.[1] This breakthrough inspired global research activity to transform the idea into practice, at the time driven mainly by the field of optical telecommunications.[2] Since then, several studies have demonstrated the potential advantages of photonic crystals for other applications, such as light emitting diodes, [3] lasers, [4,5] wave guides, [6,7] photocatalysts, [8] displays, [9,10] and solar cells. [11][12][13] In particular, the inverse silicon opal (i-Si-o) with a high refractive-index contrast has attracted attention because of its demonstrated complete photonic band gap at 1.5 mm and the possibility of large-scale synthesis.[14] While the optical properties of i-Si-o have been thoroughly investigated, [15,16] little research has been focused on its electrical behaviour, knowledge that would underpin the development of any kind of electro-optical device based on i-Si-o. It can be envisioned that the electrical properties of i-Si-o with its 3D open-framework microstructure could be very different from that of Si thin films, similar to the different behaviour observed for electrochemically etched porous silicon.[17] It is therefore our opinion that the electrical properties of i-Si-o need to be elucidated, as this data will be critical for applications such as optically amplified silicon solar cells. [18] The purpose of the work described herein is to understand the electrical properties of i-Si-o, focusing in particular on the influence of the photonic-crystal lattice constant and the effect of crystallinity and hydrogen-plasma passivation of Si on the electrical conductivity of i-Si-o, and how these material properties correlate with the optical properties of i-Si-o.To reach our objectives, we fabricated i-Si-o by infiltrating the voids of a silica-opal template with Si using chemical vapor deposition (CVD), and subsequently etching the silica spheres with hydrofluoric acid (HF).[19] Accurate measurements of the dc electrical dark conductivities (s d ) require electrodes and electrical contacts on the i-Si-o films. Therefore, instead of using glass substrates, which are most commonly employed, we prepared all samples on sapphire substrates due to their high stability against HF etching. Note that the i-Si-o fabricated on glass substrates usually gets detached and becomes free-standing after HF etching, while high-quality intact i-Si-o films can be achieved on sapphire substrates.The as-deposited Si obtained by CVD in the interstitial voids of silica opals is amorphous. We denote them inverse amorphoussilicon opals (i-aSi-os). In order to integrate i-aSi-o in optical, electro-optical, or electrical devices, it is important to achieve inverse crystalline-silicon opals (i-cSi-o), because crystalline silicon has a much higher conductivity than amorphous s...