The high versatility and ease of electrospinning of polymer solutions have recently resulted in electrospun fibers, which are of interest for a wide variety of chemical and biomedical applications. This is partially due to the high surface area of the fibers, which is attractive for the detection and capture of (bio)chemicals. In the present work, polystyrene (PS) fibers were electrospun and coated with cationic poly(allylamine hydrochloride) (PAH) or anionic dextran sulfate sodium (DSS). The fibers were physicochemically characterized. Upon incubation in a dispersion of inactivated HIV-1, avid binding of HIV to all types of fibers occurred. By atomic force microscopy and spatial selective photobleaching, the binding of the inactivated HIV-1 particles to the fibers could be confirmed. Interestingly, all fibers, especially the DSS-coated and PAH-coated ones, resulted in a significant reduction of infection of CD4(+) TZMbl cells by replication-competent HIV-1. On top, DSS-coated PS fibers were not toxic for vaginal epithelial cells, which may make these fibers of potential interest to inhibit HIV infection in the context of topical prevention. Copyright (C) 2014 John Wiley & Sons, Ltd.