Functionalized lipidic cubic phases (LCPs) have gained considerable interest as drug delivery systems (DDS) in recent years. Among their advantages, one of the most intriguing features that make them interesting as DDS is the possibility of controlling the release of drugs based on electrostatic interactions. Here modulation of the release of a positively charged drug, doxorubicin (DOX) is obtained by incorporation of small amounts of designed charged derivatives of the monoolein host lipid as additives to the otherwise non-charged LCP. By design, the charged hydrophilic head group of the additive is exposed to the aqueous channels, whereas the hydrophobic tail is incorporated in the lipid bilayer and forms an integral part thereof. Our results show that in vitro DOX release profiles can be modulated by the electrostatic interactions between the drug molecule and the charged LCP used. We demonstrate that monitoring shifts of the voltammetry peak potentials gives a unique opportunity of following even subtle changes of pH inside the aqueous channels of the cubic mesophase, while measurement of the peak current allows establishing the release profile of the drug from the dopant-modified mesophase. Small angle X-ray scattering (SAXS) data confirm that the behavior of DOX in the mesophase was not dependent on the LCP symmetry, as it remains unchanged, but rather on the charges delineating the water channel compartment.