In this comparative study, the performance of liquid-phase microextraction and electromembrane extraction in prototype equipment was evaluated for extraction of ninety basic substances from plasma. Using a commercial EME device based on conductive vials enabled a standardized and comprehensive comparison between the two methods. Extractions were performed from a pH-adjusted donor solution, across an organic liquid membrane immobilized in a porous polypropylene membrane, and into an acidic acceptor solution. In LPME, dodecyl acetate was used as the extraction solvent, while 2-nitrophenyl octyl ether was used for EME with an electric field applied across the system. To assess the extraction performance, extraction recovery plots and extraction time curves were constructed and analyzed. These plots provided insights into the efficiency and effectiveness of LPME and EME, allowing users to make better decisions about the most suitable method for a specific bioanalytical application. Both LPME and EME were effective for substances with 2.0 < log P < 4.0, with EME showing faster extraction kinetics. Small (200 µL) and large vials (600 µL) were compared, showing that smaller vials improved kinetics markedly in both techniques. Carrier-mediated extraction showed improved performance for analytes with log P < 2 in EME, however, with some limitations due to system instability. This is, to our knowledge, the first time LPME was performed in the commercial vial-based equipment. An evaluation of vial-based LPME investigating linearity, precision, accuracy, and matrix effects showed promising results. These findings contribute to a general understanding of the performance differences in vial-based LPME and EME.