Polystyrene-maleic anhydride copolymer (PSMA, M-upsilon = 700 kDa) was synthesized and efficiently processed into 400 to 600 rim diameter fibers via electro-spinning from either 20 wt % dimethylformamide or 25 wt % dimethylsulfoxide solution. Crosslinking of PSMA was effective by adding glycerol and poly(vinyl alcohol) (PVA) (M-w = 31-50 kDa) in the dimethyl formamide and dimethylsulfoxide solutions, respectively. The PSMA fibers containing glycerol at 29.4 mol% were auto-crosslinked whereas those with 12.9 mol% (2 wt %) glycerol and 15.4 mol% (0.75 wt %) PVA required heating to induce intermolecular esterification. Heat-induced crosslinking with glycerol was more effective in rendering the PSMA fibrous membranes insoluble in all solvents whereas that with PVA remained soluble in most solvents except for acetone and tetrahydrofuran. The crosslinked fibrous membranes had improved thermally stability and retained physical integrity upon exposure (2 hr at 40 degrees C) to carbon disulfide, the solvent for Friedel-Craft reactions of the styrene moiety. Hydrolysis (0.01N NaOH) of the auto-crosslinked fibrous membrane significantly improved its hydrophilicity by reducing the water contact angles from 90.6 degrees to 62.5 degrees in a matter of seconds. These ultra-high specific surface PSMA fibrous membranes have shown superior organic and aqueous solvent compatibility to be used as highly reactive and easily retrievable supports for solid-phase synthesis. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 784-793, 2009