Short pieces of fused silica capillary tubing were used to support an electrified liquid–liquid interface. A methyl deactivated silica capillary having a diameter of 25 μm was filled with 1,2-dichloroethane solution and served as the organic part of the liquid–liquid interface. A nondeactivated fused silica capillary having a diameter of 5, 10, or 25 μm was filled with an aqueous HCl solution and served as the aqueous part of the electrochemical cell. For the latter, silanization of the capillary interior with chlorotrimethylsilane allowed for a successful phase reversal. All capillaries were characterized by ion transfer voltammetry using tetramethylammonium cation as a model ion. This simple, fast, and low-cost miniaturization technique was successfully applied for detection of the antibiotic ofloxacin.