This review aims to critically analyze the current state of knowledge in the emerging field of chemical reactivity at aqueous interfaces. The area has evolved rapidly since the discovery of the so-called "on-water catalysis" effect, alluding to the fact that many chemical reactions experience a dramatic acceleration at the surface of water or different aqueous interfaces with hydrophobic media. The immense importance of this phenomenon is discussed first by reviewing some critical experimental studies in the fields of atmospheric and synthetic organic chemistry, as well as related research exploring the origins of life. The physicochemical aspects of the topic are analyzed afterwards. First, with a concise analysis of issues such as the structure, the dynamics, and the thermodynamics of adsorption/solvation processes at aqueous interfaces.Then, presenting the basic theories intended to explain interface catalysis, followed by the results of advanced ab initio molecular dynamics simulations. Though some topics addressed here have already been the focus of previous reviews, their interconnection across diverse disciplines has not been sufficiently highlighted in the literature. For this reason, this manuscript seeks to provide a common perspective by trying to identify the most fundamental issues still incompletely understood in this fast-moving domain.

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