The SiOxCyHz layers synthesized by means of the atmospheric pressure glow-like DBD assisted PECVD technology show remarkable planarizing film properties, observed for the first time. The films were deposited in a roll-to-roll mode on large area polymeric webs using HMDSO and air as the precursor and oxidiser. FTIR analysis show the carbon content in the SiOx films is strongly correlated with the precursor flow rate resulting in SiO2-like layers with negligible carbon content at lower flow values (0.4 g/h), while at higher flow rates carbon rich SiOxCyHz films were obtained. Detailed AFM surface profile analysis show that the SiOxCyHz films smoothen out the global and local surface structures of the polymer comprising a reduction in rms surface roughness (0.99 ± 0.11 nm) and increase of roughness exponent (α = 0.97 ± 0.02) compared to that of PEN polymer. These ultra-smooth organic layers together with the smooth inorganic SiOx layers (1.75 ± 0.12 nm), exhibiting roughness comparable to the polymer (1.50 ± 0.07 nm) at lower precursor input, provide an efficient route to fabricate multilayer hybrid structures in a single chamber synthesis.