Ionic inclusion inside thin conducting polymer (CP) film is a major and common feature for actuator as well as membrane-based drug release. In this study, an electro-active polymeric thin-film system has been conceptualized. PNP-electro-neutrality (Poisson-Nernst-Planck) based modeling framework with customized boundary conditions is used to depict the electrochemical phenomena. In dynamic model, kinetics of probable redox reactions is included along with electromigration and diffusion terms in the overall PNP framework. At steady state, interfacial voltage seems to hold the critically important role, while ionic migration and reaction kinetics play very crucial roles in determining the dynamics of such systems. The validated model predicts that lowering in the standard potential of the polymeric electrode accelerates the process of ionic ingress. Higher ionic flux is obtained using slower voltage scan. Variation of diffusivity shows the large spectrum of relatively unexplored dynamics for such electro-active thin-film-based system. The significance is in designing actuator- or membrane-based controlled molecular release systems. POLYM. ENG. SCI., 48:22292237, 2008. (C) 2008 Society of Plastics Engineers