Microfluidic oxygenators promise to advance extracorporeal membrane oxygenation (ECMO) devices with enhanced hemodynamics and low prime volume. We are developing a silicon-based membrane oxygenator that will offer improved gas transfer and fluid flow control. Polyethylene glycol (PEG) has been used to improve hemocompatibility by providing excellent resistance to protein adsorption. Here, we characterized a polyethylene glycol surface modification of composite silicon–PDMS membranes to evaluate their effects on microfluidic oxygenator properties. X-ray photoelectron spectroscopy (XPS) and water contact angle goniometry confirmed successful PEG attachment, evidenced by the presence of characteristic C-O bonds and increased hydrophilicity, which was stable for 2 weeks. Oxygen flux tests demonstrated gas transfer rates as high as 89.6 ± 17.9 mL/min/m² and 50.8 ± 11.7 mL/min/m² for unmodified and PEG-coated membranes, respectively. Protein adsorption studies with human serum albumin (HSA) demonstrated a significant reduction in nonspecific protein binding on PEG-coated membranes with values as low as 14 ± 6 μg/cm². These studies expand on the characterization of our engineered oxygenator membranes and provide insight for the development of future surface optimization strategies to enhance hemocompatibility.