Charge transfer phenomena at the interface between two immiscible electrolyte solutions (ITIES) are electrochemical reactions taking place in soft media. Owing to their liquid nature, the ITIES shows a large panel of electrochemical reactions including electron transfer reactions, ion transfer reactions, coupled electron–ion transfer reactions or biomimetic redox reactions. Nevertheless, the mechanisms by which these reactions proceed are yet to be fully understood. The goal of this short review is to summarise the work accomplished over the past decades towards the elucidation of the structure and reactivity at the ITIES, highlighting the main questions still to be answered.