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The field of soft wearable bioelectronics requires materials that are flexible, stretchable, biocompatible, and capable of being used over long durations. Although polydimethylsiloxane (PDMS) is one of the most commonly used substrates for these devices due to its biomimetic properties compared to biological tissues, its intrinsic hydrophobicity causes it to underperform in biological environments. In this work, a hydrophilic, stretchable PDMS electrospun fibrous mat is developed to overcome this limitation by incorporating the amphiphilic polymer polyethylene glycol block copolymer (PEG‐BCP) into the porous PDMS matrix. The nonwoven hydrophilic silicone mat shows apparent improvement in stable hydrophilicity, indicated by a significant decrease in water contact angle (from 125° to 51°) for 7 days, along with improved cellular adhesion and enhanced breathability. The PDMS‐PEG fibers show higher cell proliferation than unmodified PDMS fibers, suggesting potential for long‐term biological applications. The fibrous mat also maintains its structural integrity under mechanical stress, demonstrated by a stretchability of up to 308.8% strain with reduced adhesion forces. This novel material surpasses previous PDMS fibrous substrates and enables electroless gold plating, providing a promising future for wearable fibrous electronics and biomedical devices featuring hydrophilic, stretchable, conductive, and biointegrated materials.