The synthesis of PANI/Ag hybrid materials has been carried out via a rapid chemical oxidative, in-situ polymerisation method, using silver nitrate and ammonium peroxydisulfate as oxidant precursors. These species react together to produce Ag2+, an oxidising intermediate which has greater oxidising power than either persulphate or Ag+ alone. The reaction thus proceeds at a much accelerated rate than that of pure PANI, approximately 6 times faster. Various characterisation techniques were used to characterise this new hybrid material, PANI-Ag. UV-vis absorption spectroscopy was used to follow the formation of polymer over time and monitor the rate at which the reaction progresses for both PANI and PANI-silver. It is evident from the absorption spectra that the polymer forms via the fully-oxidised pernigraniline state initially, before reducing back into the more stable emeraldine salt form. This process is significantly accelerated using both APS and AgNO3, as opposed to when using APS or AgNO3 alone. These new composites could potentially find use as functional materials for the printed electronics industry where new processable, hybrid materials as required for applications in sensing, memory, logic and photovoltaics.