Molecular self-assembly is known to provide a powerful tool for creating functional structures, with the ultimate structure and functionality encoded in the molecular building blocks. Upon molecule deposition onto surfaces, functional structures have been created ranging from defect-free, highly symmetric two-dimensional layers to complex assemblies with dedicated functionality. Especially organic molecules play a key role for molecular self-assembly due to their impressive structural flexibility and the high degree of control by chemical synthesis. Furthermore, the surface itself provides another exciting dimension: adjusting the subtle balance between intermolecular and molecule-surface interactions allows creating a broad variety of structures and explains the great success when confining molecular self-assembly to surfaces. While most of the structures realized so far have been fabricated on metallic substrates, comparatively little is known about molecular self-assembly on insulating surfaces. However, extending the materials basis to insulating substrates is of increasing interest to benefit from self-assembly strategies for emerging technologies such as molecular (opto)electronics. For the latter and further related applications, decoupling of the electronic structure from the underlying substrate is mandatory for the device functionality. Moreover, future applications will require the molecular structure to be stable at room temperature rather than at low temperatures. On insulating support surfaces, however, most attempts to create self-assembled molecular structures at room temperature have been hampered by the weak molecule-surface interactions. Thus, considerable effort has been made to establish means for increasing