By employing the new methodology of entrapment of organic molecules within metals, we demonstrate the ability to modify the conductivity of a metal by suitable polymer entrapment. Specifically, polyaniline (PANI) in two molecular weights was entrapped in silver at different concentrations and a comprehensive comparison was preformed for a range of the composite properties, characterized by XRD, SEM, BET, TGA, and density measurements. Pressed films were utilized to measure the electrical conductivity of the composites in order to study the PANI-silver interactions at the molecular level and to establish a correlation between the microscopic morphology and the film conduction. Such correlations have been identified, and are interpreted. This work extends the functional applications of the new metallic composites and offers insight on the polymer-metal molecular level interactions.