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In this paper, we have explored Parylene-C (PC) as a sensing material for its unique signature and selectivity for explosive sensing. We have used a bi-layer deposition process to fabricate bottom-gate-top-contact organic field effect transistor (OFET) structures. Opening of dangling bonds on subjecting PC to plasma oxidation (POPC) renders these molecules to be employed as a receptor material in sensing vapors of both explosives and non-explosives, such as Trinitrotoulene (TNT), 1,3,5 trinitro-1,3,5-triazacyclohexane(RDX), PETN, Dinitrobenzene (DNB), Nitrobenzene (NB), Benzoquinone (BQ), and Benzophenone (BP). The change in: 1) the vibrational modes of the molecule by infrared spectroscopy; 2) surface potential of POPC by Kelvin probe force microscopy (KPFM); and 3) electrical characterization by I-V measurements of PC-based OFET on exposing to vapors have been systematically studied. Different signatures for all the analytes have been observed while exact and perfect selectivity for TNT, RDX were found from I-V studies and for PETN by KPFM studies. Thus, the OFET device-based chemical sensors demonstrated here with improved sensitivity and excellent selectivity, stand as promising candidates for explosives detection.