Poly(methyl methacrylate) (PMMA) nanofibers containing the inclusion complex forming betacyclodextrin (_-CD) were successfully produced by means of electrospinning in order to develop functional nanofibrous webs for organic vapor waste treatment. Electrospinning of uniform PMMA nanofibers containing different loadings of _-CD (10%, 25% and 50% (w/w)) was achieved. The surface sensitive spectroscopic techniques; X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that some of the _-CD molecules are present on the surface of the PMMA nanofibers, which is essential for the trapping of organic vapors by inclusion complexation. Direct pyrolysis mass spectrometry (DP-MS) studies showed that PMMA nanowebs containing _-CD can entrap organic vapors such as aniline, styrene and toluene from the surroundings due to inclusion complexation with _-CD that is present on the fiber surface. Our study showed that electrospun nanowebs functionalized with cyclodextrinsmayhave the potential to be used as molecular filters and/or nanofilters for the treatment of organic vapor waste and air filtration purposes.