Biopolymers, such as deoxyribonucleic acid-hexadecyltrimethyl ammonium chloride (DNA-CTMA) and bovine serum albumin-polyvinyl alcohol (BSA-PVA), were studied using a novel capacitive test structure. A variety of external electrical stimuli were applied, including a low frequency alternating current signal and a rf/microwave frequency signal combined with a DC bias. The dynamic responses of the DNA-based biopolymer to the external stimuli are presented in this paper. The electrical transport measurements support the space-charge-limited conduction and the low frequency capacitance–voltage (CV) measurements showed large depletion layer capacitance at the Au–biopolymer interface, at 20 Hz, and the capacitance approaching bulk values at 1 MHz. Electric force microscopy (EFM) was utilized for visualization of charge dynamics and to examine the effect of DC bias combined with an AC signal. Ionic charges in the DNA-CTMA system seem to be responsible for the dynamic response to the various external electrical stimuli.