A novel chemical-sensing technique to detect the nerve agent sarin stimulant dimethylmethylphosphonate (DMMP) is presented. This technique uses a combination of doped polypyrrole as an active chemical material coated on an optical fiber to form an intrinsic fiber-optic sensor. Sensitivity of up to 26 ppm of DMMP with response time of a few seconds is demonstrated. Influence of three different dopants, i.e., 1,5 naphthalene disulphonic acid, anthraquinone 2 sulphonic acid, and hydrochloric acid is investigated for sensor response and sensitivity. Two polymer processing techniques, i.e., in situ deposition and monomer vapor phase deposition is investigated for optimal polypyrrole morphology for DMMP sensitivity. The influence of substrate, nature, i.e., hydrophilic and hydrophobic, on sensor sensitivity is studied. Organophosphate specific binding sites have been created in polypyrrole structure using Cu2+ ions to enhance DMMP response. The selectivity issue is addressed by testing the sensor in the presence of other gases like ammonia, water vapor, and acetone which influence the electronic properties of polypyrrole.