A novel atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) approach toward the growth of conventional polymer layers is characterized and interpreted. A set of three methacrylate monomers (methyl, butyl, and glycidyl methacrylate) were investigated using ultrashort plasma discharges (ca. 100 ns) pulsed at various frequencies, covering a range of duty cycle from 0.1% to 0.000 316%. An unprecedented weight-average molar mass of 94 000 g mol(-1) coupled to an outstanding thin film conformality and an excellent chemical functionalities retention was achieved for the best deposition conditions. Insights into the growth mechanisms in AP-PiCVD and their dependence on the monomer's intrinsic properties are provided.