Polyoxometalates (POMs), an exceptional family of coordination clusters consisting of Mo, W, V, etc. early transition metal ions in their highest oxidation states, have received significant attention over recent years due to their structural versatility and unique and diverse chemical and physical properties. The functionalization of POMs with organic ligands provides a novel strategy to precisely incorporate POMs with advanced functional organic moieties on their surfaces and enhance their compatibility in organic media. Among the various organically functionalized synthetic strategies for POM-based organic–inorganic hybrid materials, alkoxylation of POMs stands for one of the hottest topics during the past decades, since the diverse and tunable alkoxyl ligands are able to anchor on the surface of many POMs clusters, forming novel and flexible organically functionalized POM clusters, which can be further exploited as building blocks to design various functionalized POM-based hybrids with charming catalytic properties, and biomedicine, energy, or functional materials applications. In this review, recent advances in alkoxylation chemistry of POMs from synthetic strategies, structural overviews to their functional applications have been discussed.

多金属氧酸盐（POM）是由Mo，W，V等处于最高氧化态的早期过渡金属离子组成的特殊配位簇家族，由于其结构的多功能性以及独特而多样的化学和物理性质，近年来受到了广泛的关注。特性。具有有机配体的POM的功能化提供了一种新颖的策略，可以精确地将具有高级功能有机部分的POM并入其表面，并增强其在有机介质中的相容性。在基于POM的有机-无机杂化材料的各种有机功能化合成策略中，POM的烷氧基化是过去几十年来最热门的主题之一，因为多样且可调的烷氧基配体能够固定在许多POM簇的表面上，形成新颖且灵活的有机功能化POM簇，可进一步利用它作为构建基来设计各种具有迷人催化特性的生物功能，基于POM的杂化材料以及生物医学，能源或功能材料应用。在这篇综述中，已经讨论了从合成策略，结构概述到其功能应用的POM烷氧基化化学的最新进展。