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A thesis submitted in fulfillment of the requirements for the degree of Doctor of Philosophy in Material Physics., Extremely high electron mobility as well as its low dimensionality makes the graphene a good candidate to be incorporated in future organic-devices such as field effect transistors (FET). However, prior to its implementation a band gap must be introduced in the graphene. Towards this end, one of the most promising strategies is quantum confinement, i.e. shrinking the size of the graphene into smaller structures such as graphene-nanoribons (GNR), where the band gap is controlled by the lateral confinement of the final structure. The surface assisted Ullmann coupling allows the synthesis of said GNRs. However, reasonable reaction yields and sufficiently extended GNRs can so far only be realized on coinage metals where the GNRs properties are inherently coupled to the surface and therefore inaccessible for device applications such as the FET. Consequently, the next step forward in the field either requires the larger scale synthesis of GNRs for ex situ transfer protocols onto more suitable substrates or the in situ synthesis of GNRs directly on technologically relevant surfaces. Here, we synthesize poly-p-phenylene (PPP) wires, the smallest possible GNR, via the Ullmann coupling reaction on three unconventional surfaces. We achieve the first PPP synthesis on a magnetic template, where it is demonstrate that the intermixing of elements in the bimetallic GdAu2 surface alloy is a viable strategy to improve the reaction conditions by synergistic effects while maintaining the extraordinary alignment and extensions of individual PPP generally only achievable on Au (111) surfaces. Another strategy to optimize the reaction conditions and alignment of GNRs is the use of surface steps. We employ a curved Au (111) crystal, where the surface step density is continuously varied across the same sample, to synthesize PPPs. The comparison of the reaction on different parts of the crystal performed under identical conditions, such as reaction temperature and molecule coverage, allows us to unambiguously isolate the influence of the steps. The central finding is a lowering of the reaction temperature by 25 K when using the right kind of surface step orientation and density. In the last chapter, we demonstrate the formation of PPP wires on the dielectric TiO2 (110) surface, a model surface for the realization of a FET. Optimized reaction temperatures and yields are achieved when an external catalyst is employed while simultaneously suppressing unwanted side reactions. The on-surface synthesized PPPs offer the possibility of characterization by wellestablished surface science techniques. Specifically, we employ scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) to elucidate geometric structures of the PPPs, angle resolved photoemission spectroscopy (ARPES) to probe the valence band of the PPPs and x-ray photoelectron spectroscopy ( XPS), the core technique of this work, to study reaction yields and mechanisms. The combination of our design strategies and the experimental multi-technique approach has established novel substrates for the realization of next generation GNR-based devices such as the FET.