By a Plasma Enhanced Chemical Vapor Deposition process (PECVD), we are able to prepare nitrogenated amorphous carbon materials around room temperature from methane and nitrogen gas as precursors. We have also used chlorine gas as an additive to reduce the hydrogen content of our samples. Starting from the “as-deposited” materials, we have investigated their thermal stability by successive heat treatments up to 1400 °C. These compounds suffer a weight loss mostly due to the hydrogen departure. They become nonfusible and it turns out that nitrogen, chemically bound to sp2 hybridized carbons, induces some changes in the physical properties. In order to understand the relationship between the local structural organization and the physical characteristics, we have investigated different spectroscopic techniques such as Nuclear Magnetic Resonance, IR Absorption, and X-ray Photoelectron Spectroscopy. We have also investigated several transport properties: (i) The dc electrical conductivity shows a kind of metal/insulator transition around 700 °C. The temperature dependence for the conductive samples gives evidence for a pseudogap associated with the presence of localized states, (ii) The thermal conductivity exhibits, for the as-deposited compound, a very low value varying slowly with temperature; its magnitude as well as its temperature dependence, characteristic of noncrystalline materials, are modified by the annealing process. Finally, an electronic band model is proposed, explaining the structural evolution through a kind of Mott–Anderson pseudotransition.