Plasma-deposited PEG-like films are emerging as promising materials for preventing protein and bacterial attachment to surfaces. To date, there has not been a detailed surface analysis to examine the chemistry and molecular structure of these films as a function of both precursor size and structure. In this paper, we describe radio-frequency plasma deposition of a series of short-chain oligoglymes, dioxane, and crown ethers onto glass cover slips to create poly(ethylene glycol)-like coatings. The resultant films were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), dynamic contact angle goniometry, and radiolabeled fibrinogen adsorption. Detailed analysis of the high-mass (120-300 m/z) TOF-SIMS oligoglyme film spectra revealed six classes of significant fragments. Two new models are proposed to describe how these fragments could be formed by distinct film-building processes: incorporation of intact and fragmented precursor molecules. The models also provide for the incorporation of hydrocarbon - a species that is not present in the precursors but is evidenced in XPS C-1s spectra of these films. Two additional models describe the effects of incorporating intact and fragmented cyclic precursors.