Electroless nickel (EN) plating is a practical solution for coating underground buried pipelines, as it produces coatings with good corrosion and wear resistance, good adhesion, and uniform thickness. Owing to the versatility of the EN technique, co-depositing nanoparticles such as cobalt (Co) and polytetrafluorethylene (PTFE) can enhance the properties of the protective coating. Moreover, EN plating may be deposited in separate baths or combined, resulting in multilayered or composite coatings. Therefore, this work will focus on the systemization of the multilayered and composite electroless Ni-Co-P-PTFE coatings on mild steel, as well as the inspection of the post-heat treatment effect. Microstructural characterization is then examined using surface analysis techniques, namely X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and confocal laser scanning microscopy. The magnetic, scratch hardness, micro-hardness, and corrosion resistance properties of the multilayered and composite coatings are also compared.