The continued evolution of functional materials that contribute to pressing societal challenges requires the development of powerful synthetic methodologies in polymer systems. Since their discovery by Staudinger in the early 20th century, the unique chemistry of ketenes have fascinated synthetic chemists and been the driver of revolutionary applications in photolithography, medicinal chemistry, and commodity materials. The versatile chemistry of ketenes, specifically their ability to act as an electrophile and/or undergo cycloaddition reactions, has recently been shown to provide a powerful platform for the design of next-generation materials. This Highlight focuses on the history of ketenes in materials science and their recent renaissance in polymer chemistry, with specific focus being given to methodologies that provide reliable access to this important functional group in polymer systems. (C) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3769-3782