2D conjugated coordination polymers (cCPs) based on square-planar transition metal-complexes (such as MO₄, M(NH)₄, and MS₄, M = metal) are an emerging class of (semi)conducting materials that are of great interest for applications in supercapacitors, catalysis, and thermoelectrics. Finding synthetic approaches to high-performance nickel-nitrogen (Ni-N) based cCP films is a long-standing challenge. Here, a general, dynamically controlled on-surface synthesis that produces highly conductive Ni-N-based cCP films is developed and the thermoelectric properties as a function of the molecular structure and their dependence on interactions with ambient atmosphere are studied. Among the four studied cCPs with different ligand sizes hexaminobenzene- and hexaaminotriphenylene-based films exhibit record electrical conductivity (100–200 S cm^–1) in this Ni-N based cCP family, which is one order of magnitude higher than previous reports, and the highest thermoelectric power factors up to 10 µW m^–1 K^–2 among reported 2D cCPs. The transport physics of these films is studied and it is shown that depending on the host-guest interaction with oxygen/water the majority carrier type and the value of the Seebeck coefficient can be largely regulated. The high conductivity is likely reflecting good interconnectivity between (small) ordered domains and grain boundaries supporting disordered metallic transport.