“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c13630. Materials and chemicals, preparation of the electrodes, electrowetting setup configuration, PTFE cell configuration, synthesis and NMR spectra ( 1 H, 13 C, 19 F, and 7 Li) of EMIM-TFSI, surface tension and mass density measurements, electrochemical measurements, calculation of capacitance from electrochemical impedance measurements, contact angle measurements, in situ Raman spectroscopy measurements, predicting the electrowetting response using the Y−L equation, contact angle variations upon deep intercalation/deintercalation in EMIM-TFSI, surface electrochemistry of LiClO 4(PC) in hexadecane, interfacial surface tension and work of adhesion at the liquid−liquid interface, dynamic measurements in the biphasic systems, electrowetting under AC in the biphasic systems, optical images of the droplets at selective potential biases for the systems under study, and electrowetting performance of selected biphasic systems reported in the literature (PDF) Changes in apparent contact angle during 200 wetting/ dewetting cycles for a 1 M LiClO 4(PC) droplet on HOPG in air (MP4) Changes in apparent contact angle at the EMIM-TFSI| HOPG interface in air upon application of a constant potential pulse for 200 s at +1.7 V with subsequent stepping to 0 V (MP4) Changes in apparent contact angle at the 20 m LiTFSI (aq) |HOPG interface in air upon application of a constant potential pulse for 200 s at +0.8 V with subsequent stepping to 0 V (MP4) Changes in apparent contact angle during 200 wetting/ dewetting cycles following the protocol described in the Experimental Section, for a 1 M LiClO 4(PC) droplet on HOPG in hexadecane (MP4) Changes in apparent contact angle during 200 wetting/ dewetting cycles following the protocol described in the Experimental Section, for a 20 m LiTFSI (aq) droplet on HOPG in hexadecane (MP4)…”