The cocrystals of two reagents of mismatch solubility, hydrophilic caffeine and lipophilic 1-hydroxy-2-naphthoic acid, were obtained at a water-oil interface. 1 By analysing the product collected at the phase interface by X-ray diffraction and Raman spectroscopy, we confirmed that we obtained the molecular cocrystals of caffeine and 1-hydroxy-2-naphthoic acid, free of starting reagents and solvents. Polarisation of the interface allowed the electrochemical control of the cocrystallisation process: for non-polarised interfaces, a mixture of phase I and II cocrystals were obtained, whereas cocrystals of phase I were formed when a high interfacial potential was applied. The difference between the polymorphs obtained in the absence or in the presence of interfacial polarisation is attributed to the different cocrystallisation mechanisms. In the absence of interfacial polarisation, caffeine and 1-hydroxy-2-naphthoic acid are cocrystallising through an interfacial process. When the interface is positively polarised, cationic form of caffeine is transferred to the organic phase, the complex with naphthoic acid is formed and the proton is released. The pH increased after cocrystallisation, suggesting that the liberated H+ remained in the organic phase. On the contrary, in the absence of polarisation or in the case of low interfacial potential the protons are remaining in the aqueous phase what resulted in a decrease in pH after cocrystallisation process. We demonstrated an indirect evidence of the transfer of caffeine upon chemical polarization of the interface. We observed almost no deposits in the organic phase by analysing it with a scanning electron microscope. We investigated here the mechanism behind the formation of cocrystals by using the polarized interface between two immiscible electrolyte solutions (ITIES).2 For the purpose of this study, the two solutions have been placed in contact3 : one being an aqueous solution of caffeine, as a model drug substance, and the second being organic solution of 1-hydroxy-2-naphthoic acid (cocrystal component) and the salt inducing the suitable imposed potential difference. The formation of the caffeine: 1-hydroxy-2-naphthoic acid complex was studied by changing the salts present in the aqueous phase, the chemical compounds imposing potential in organic phase, varying the organic solvents and the temperature at the liquid-liquid interface. The cocrystals collected at the interface were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and low frequency Raman spectroscopy. We studied the proportions of polymorphic phases as a function of changing conditions. To understand the mechanism behind the caffeine transfer and the formation of different forms of polymorphic crystals at the water-oil interface, Electrochemical Noise Experiments4 have been carried out. A four-electrode system was used to apply zero volts between the working electrode and the counter electrode and then measuring the current and the potential versus the reference electrode. Such a setup allows the measurement of potential and current as the function of time simultaneously. We could thus follow the phenomena that are taking place at the interface. The measurements were carried out by varying the cations (tetraalkylammoniums, Li+, K+) in aqueous and organic phase as well as the anions (derivatives of tetrakis(phenyl-borate) in organic phase). The experimental results were supported by theoretical equations and applied to the system containing caffeine. This novel strategy of cocrystallization, was followed by the investigation of other coformers (3-hydroxy-2-naphthoic acid) and drugs (cocrystals of ketoprofen with amino acids and carboxylic acids) in order to validate the method. Such an electrocrystallization process at the ITIES will open new opportunities for the formation of drugs cocrystals. M. Kaliszczak et al., CrystEngComm (2022) doi: 10.1039/D1CE01281A. Z. Samec, Pure Appl. Chem., 76, 2147–2180 (2004). S. J. Diez et al., Cryst. Growth Des., 18, 3263–3268 (2018). I. B. Obot, I. B. Onyeachu, A. Zeino, and S. A. Umoren, J. Adhes. Sci. Technol., 33, 1453–1496 (2019).