A recently developed technique termed 'Electrochemical Optical Waveguide Lightmode Spectroscopy' (EC-OWLS) combines evanescent-field optical sensing with electrochemical control of surface adsorption processes. Initial EC-OWLS investigations efficiently monitored molecular surface adsorption and layer thickness changes of an adsorbed polymer layer examined in situ as a function of potential applied to a waveguide1. A layer of indium tin oxide (ITO) served as both a high refractive index waveguide for optical sensing, and a conductive electrode; an electrochemical flow-through fluid cell incorporated working, reference and counter electrodes. Poly(L-lysine)- grafted-poly(ethylene glycol) (PLL-g-PEG) served as a model, polycation adsorbate. Results indicate that adsorption and desorption of PLL-g-PEG from aqueous buffer are a function of applied potential, and that binding events subsequent to PLL-g-PEG functionalization are dependent on reorganization in the molecular adlayer.