The coating of materials with diamond-like carbon (DLC) is a very common way to change and improve their basic characteristics. Although DLC is used on several substrates, the chemical and physical properties throughout the coating process on plastics are yet sparsely investigated. Two types of protective coatings one sp3-enriched (robust, r-type) and one with more sp(2)-centers (flexible, f-type) have been realized on polyethylene by PECVD deposition. SEM and AFM analysis of coated samples of DLC types revealed diverse surface topographies on different scales and images appeared even differently smoothed by the carbonaceous deposits. Grains of both DLC types are platelet-shaped and nearly double in size for the robust type indicating fundamental differences in the epitaxial DLC growth. NEXAFS spectroscopy showed significant details of carbon centers in chemically different neighborhood displaying a characteristic fingerprint behavior. Comparison of deposition models revealed a mechanism of interlayer formation which is discussed in detail. Interlayer formation is clearly the appropriate explanation of the process for the current carbon deposition between these two unequal materials. An improved understanding of hard DLC and soft polyethylene assembly is given in the presented work. (C) 2013 Elsevier B.V. All rights reserved.