In this study, we report the use of surface plasmon spectroscopy (SPS) to investigate the self-assembly polymer solution adsorption process in situ. A sealed sample cell made of Teflon was assembled with the substrate initially coated with a positively charged surface using the Langmuir-Blodgett-Kuhn (LBK) deposition technique. The cationic and anionic polymer combinations were comprised mainly of a class of polyelectrolytes called ionenes and several anionic polymers. The solution adsorption process generally showed linear behavior except were the deviation is attributed to a poorly charged initial layer. The adsorption behavior is postulated to be due to conformational requirements and charge distribution of the individually adsorbed polymers. The time of adsorption for each polymer pair was also investigated. The technique promises to be an important tool in determining the mechanism for these types of adsorption processes.