Modifications to the space charge region of p+ and p-GaAs due to surface charge modulation by the pH-induced deprotonation of bound carboxylic acid terminal monolayers were studied by electrochemical impedance spectroscopy and correlated to flat-band potential measurements from Mott-Schottky plots. We infer that the negative surface dipole formed on GaAs due to monolayer deprotonation causes an enhancement of the downward interfacial band bending. The space charge layer modifications were correlated to intermolecular electrostatic interactions and semiconductor depletion characteristics.