This study focuses on the fabrication of plasma-polymerized polyethylene glycol (pp-PEG) with porous morphology in a pulsed dielectric barrier discharge (DBD) plasma under atmospheric pressure. The signal frequency that modulates the plasma discharge was found to have a major influence on the pp-PEG film morphology. The recorded discharge current–voltage characteristic allowed us to establish a homogeneous regime of the DBD plasma operated in helium gas flow upon the frequency range 2–10 kHz. The as-prepared pp-PEG films were characterized by the Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and liquid-phase chromatography (HPLC) techniques. The performed analysis revealed that as the discharge frequency increases, the morphology of the obtained films becomes porous due to the plasma-induced stronger monomer fragmentation. To gain knowledge about the plasma species and the interaction processes that impact the film morphology, optical emission spectroscopy (OES) and intensified charge-coupled device (ICCD) fast imaging technique were applied. The determined vibrational (Tvib) and rotational (Trot) temperatures exhibit a decrease with the introduction of monomer vapors into the discharge gap. For instance, Trot drops from approximately 475 K to 350 K, and Tvib falls from 2850 K to 2650 K for a monomer vapor injection rate of 16 µL/min. This was attributed to the energy losses of the plasma-generated particles, as the inelastic collisions augment with the injection of a monomer. Concurrently with the change in temperature, the discharge current varies significantly for the investigated frequency range and exhibits a drop at high frequencies. This discharge current drop was explained by an enhancement of the recombination rate of charged particles and seems to confirm the prevalence of a plasma-induced monomer fragmentation process at high frequencies.