The application of (super)hydrophilic coatings in sectors of activity concerned by fogging, such as the food industry, the architectural sector, and medicine has attracted enormous attention over the past few years. However, despite this interest, most of the coating deposition techniques used thus far are not suitable for large-scale production because of their multistep nature. In this regard, the use of atmospheric pressure dielectric barrier discharges (AP-DBD) operated under a controlled N2/N2O atmosphere offers a promising alternative to conventional deposition techniques for the fabrication of anti-fogging coatings. Using this one-step coating approach, four siloxane precursors with different structures and different number of Si―H and Si−CH3 groups; namely, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS), octamethylcyclotetrasiloxane (OMCTS), 1,1,3,3-tetramethyldisiloxane (TMDSO), and hexamethyldisiloxane (HMDSO) were deposited on glass samples. Because of their extreme wetting behavior (WCA < 5°), TMCTS-coated glasses featured an excellent anti-fogging performance, in contrast to OMCTS-, TMDSO-, and HMDSO-coated glasses which were not fogging-resistant (WCA ≈ 80°)). Coupled with hydrophilic functionalities, such as CO, O CO, and SiOH groups, the relatively high surface roughness of TMCTS-coated glass, compared with that of OMCTS-, TMDSO-, or HMDSO-coated glass, accounted for its superior visual characteristics when exposed to water vapor at 80 °C. These results allow us to confidently conclude that the cyclic structure of TMCTS in conjunction with the high reactivity of the Si-H bonds is responsible for the observed anti-fogging effect.