The possibility for electrochemical modification of the surface functional groups of a self-assembled siloxane-anchored monolayer was explored. The primary challenge of this work was to minimize the insulating silicon oxide layer while still providing ample hydrophilic oxide for anchoring siloxane-based monolayers. Working on highly doped silicon electrodes, wetting measurements and scanning probe microscopies (both atomic force microscopy and lateral force microscopy) were combined with electrochemical measurements to evaluate various surface preparations in terms of their suitability for combining electrochemical activity with smooth uniform surfaces on which successful monolayer formation can be achieved. The difficulties encountered in achieving this balance suggest that organic electrochemistry on an oxidized silicon surface will be difficult to achieve, in the presence of even a thin oxide layer.