Plasma polymerization experiments are typically conducted by sustaining a non-thermal plasma in a gas flow containing monomer molecules. Recently, it was however observed that plasma polymerization can also occur in a nitrogen/2% ethanol vapor dielectric barrier discharge operated at medium pressure (5.0 kPa). To obtain a better understanding of this peculiar plasma polymerization behavior, a detailed parameter study is conducted in this work. The influence of plasma exposure time at fixed discharge power on the coating properties is investigated as well as the influence of discharge power applying a fixed energy density. Results reveal that at a discharge power ≥ 3.0 W, very hydrophilic (WCA values < 11°) coatings are deposited possessing N/C ratios in the range 32–38% and O/C ratios in the range 21–40%. XPS analysis shows that the coatings mainly consist out of amides, amines, imines and nitril/isonitrile groups. FTIR results confirm this conclusion and also show that the C≡N groups are mainly present as isonitriles. With increasing discharge power, a small decrease in O/C ratio is observed combined with an increasing amount of isonitriles. The investigated treatment times also do not affect the surface chemical composition nor the surface wettability suggesting excellent in-depth coating homogeneity. The plasma exposure time does however strongly affect the coating thickness: a linear increase in coating thickness with plasma exposure time is observed in this work. The obtained results thus prove that a nitrogen/ethanol vapor DBD operated at medium pressure is capable of depositing highly hydrophilic nitrogen- and oxygen-rich deposits, which can have applications in different research areas.