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The wettability of electrospun poly(ϵ‐caprolactone) (PCL) mats was improved by co‐electrospinning with poly(vinyl alcohol) (PVA), by double‐spinneret electrospinning method. The improved hydrophilicity of the hybrid PCL/PVA mats was confirmed by water contact angle measurement. The in vitro cell attachment on the hydrophobic PCL and hydrophilically modified PCL/PVA mats was compared by culture studies using human prostate epithelial cells (HPECs). The stability of water‐soluble PVA component in the electrospun PCL/PVA mats was checked by thermogravimetric analysis and intensity of fluorescence material after immersion in water for 7 days. The images from scanning electron microscopy, field emission scanning electron microscopy, and optical microscopy showed that the attachment and proliferation rate of HPECs were improved by introducing PVA into the electrospun PCL mats. © 2005 Wiley …