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Poly(o-phenylene diamine) is a polymer of PANI group. PANI is not a good processable conducting polymer to improve its processability, we chose o-phenylene diamine as a monomer. Poly(o-phenylene diamine) (PoPD) is possible to synthesized by varying reaction condition such as different acidic medium and different organic solvent medium in presence of APS as a radical initiator. Nano structure PoPD with free =NH group formed in DMSO medium and polymer with free -NH2 group was synthesized in H2SO4 medium. sulfuric acid doped polymer having free -NH2 functional group was introduced as an aliphatic alcohol sensor material. Polymer with free =NH group shows good conductivity with out doping. The nanofiber of PoPD with =NH functional group was also introduced for the sensing of higher alcohols as well as selective sensing of isoamyl alcohol.