Polyaniline (PANI)-based materials for both removal and sampling of volatile organic compounds (VOCs) from air by rapid adsorption/desorption processes have been developed. The polymer was synthesized in form of emeraldine as both salt and base using different synthetic approaches, a traditional one and a "green" one. VOCs adsorption/desorption efficiency was evaluated for all the materials analyzing the desorbed VOCs fractions by GC/MS technique and obtaining results similar to the presently adopted method employing commercial activated carbon. Most important, in this work it has been demonstrated for the first time that the use of PANI-based sorbents allowed the substitution of the toxic CS2, recommended in official methods, with the less hazardous CH3OH as the VOCs extraction solvent. Moreover, a complete regeneration of the polymers could be realized by a few rapid washing steps. Finally, the best PANT based material was subjected to recycling tests thereby showing a high adsorption/desorption efficiency retention up to four runs. (C) 2017 Elsevier B.V. All rights reserved.