The scientific community is interested in studying matter at the nanoscale and to fabricate nanomaterials that will benefit the development of our society. Within this context, the usage of organic molecules to build one-atom thick films on metal surfaces has gained special attention in the past decade due to their outstanding electronic properties for their usage in nanoelectronic devices. These nanomaterials are formed by a process known as molecular self-assembly by which the molecules bond to each other on a surface to form different two-dimensional (2D) structures.In this PhD thesis, a variety of factors that influence the formation of different 2D nanomaterials is presented by making use of data acquired by sophisticated equipment that allows the observation of matter at the nanoscale, such as the scanning tunneling microscope (STM) that was operated under ultra-high vacuum (UHV) or conditions of extremely low pressure to ensure a well-controlled environment. Therefore, with the outstanding imaging capabilities of the STM, it is possible to observe the organic molecules (in the range of a few nanometers) that form these 2D nanomaterials. This thesis focuses on a class of 2D nanomaterials that are formed by linking organic molecules with metal atoms on a metal surface, i.e., metal-organic coordination networks (MOCNs). The MOCNs offer promising applications in nanoelectronic devices due to the metal-atoms that are incorporated within the 2D structure of these nanomaterials. Furthermore, the influence of the number of molecules and the chemical structure of the organic molecules in the formation of the MOCNs is presented in detail in this work.

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